TW201735161A - Phase shift mask blank, phase shift mask and method of manufacturing a display device - Google Patents
Phase shift mask blank, phase shift mask and method of manufacturing a display device Download PDFInfo
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- TW201735161A TW201735161A TW106106563A TW106106563A TW201735161A TW 201735161 A TW201735161 A TW 201735161A TW 106106563 A TW106106563 A TW 106106563A TW 106106563 A TW106106563 A TW 106106563A TW 201735161 A TW201735161 A TW 201735161A
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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
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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
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
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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
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
Abstract
Description
本發明係關於一種相位偏移光罩基底、相位偏移光罩及顯示裝置之製造方法。The present invention relates to a phase shift mask substrate, a phase shift mask, and a method of fabricating a display device.
當前,液晶顯示裝置採用VA(Vertical alignment,垂直配向)方式或IPS(In Plane Switching,橫向電場效應)方式等。藉由採用該等方式,液晶顯示裝置明亮、省電,並且有望提高高清、高速顯示、廣視角之顯示性能。 例如,於應用該等方式之液晶顯示裝置中,對像素電極應用形成為線與間隙圖案狀之透明導電膜,為了提高顯示裝置之顯示性能,迫切期望此種圖案之進一步微細化。例如,較理想為將線與間隙圖案之間距P(線寬L與間隙寬度S之合計)自6 μm縮小為5 μm,進而自5 μm縮小為4 μm。於該情形時,大多情況下線寬L、間隙寬度S中至少任一者未達3 μm。例如,L<3 μm、或L≦2 μm、或者S<3 μm、或S≦2 μm之情況並不少見。 另一方面,就液晶顯示裝置或EL(electroluminescence,電致發光)顯示裝置中所使用之薄膜電晶體(Thin Film Transistor:TFT)而言,採用如下構成:構成TFT之複數個圖案之中形成於鈍化層(絕緣層)之接觸孔貫穿絕緣層,而導通至位於其下層側之連接部。此時,若未準確地定位上層側與下層側之圖案且未確實地形成接觸孔之形狀,則無法保證顯示裝置之正確動作。 而且,此處同樣需要顯示性能之提高及器件圖案之高集成化,而謀求圖案之微細化。即,需要使孔圖案之直徑亦低於3 μm。例如需要直徑為2.5 μm以下、進而直徑為2.0 μm以下之孔圖案,預計不久的將來甚至希望形成具有比2.0 μm更小之1.5 μm以下之直徑的圖案。 鑒於此種背景,可應對線與間隙圖案或接觸孔之微細化的顯示裝置製造用光罩之需求持續高漲。 且說,於半導體(LSI(Large-Scale Integration)等)製造用光罩之領域,存在為了獲得解像性,而開發高NA(Numerical Aperture,數值孔徑)(例如0.2以上)之光學系統與利用相位偏移作用之相位偏移光罩之情況。相位偏移光罩可與單波長之短波長光源(KrF或ArF之準分子雷射等)一併使用。藉此,可應對各種元件等之高集成化及隨之發生之光罩圖案之微細化。 另一方面,於顯示裝置製造用之微影領域,一般而言不應用上述方法進行解像性提高或焦點深度擴大。作為其原因,可列舉於顯示裝置中,所要求之圖案之積成度及微細度不及半導體製造領域。實際上,顯示裝置製造用之曝光裝置(一般作為LCD(Liquid Crystal Display,液晶顯示裝置)曝光裝置、或液晶曝光裝置等而為人所知)中所搭載之光學系統或光源亦與半導體製造用之光學系統或光源不同,相較於解像性及焦點深度,生產效率(例如,擴大光源之波長區域而獲得較大之照射光量,縮短產距等)更受重視。 若光罩之轉印用圖案微細化,則將該轉印用圖案準確地轉印至被轉印體(欲進行蝕刻加工之薄膜等,亦稱為被加工體)之步驟難以實施。其原因在於:實際生產中用於顯示裝置製造之轉印步驟的上述曝光裝置之解像極限為3 μm左右,但顯示裝置所需之轉印用圖案中,需要如上述CD(Critical Dimension:線寬)接近或低於3 μm之尺寸者。 進而,顯示裝置製造用遮罩與半導體製造用遮罩相比面積較大,故而於實際生產中,將具有未達3 μm之CD之轉印用圖案面內均一地加以轉印存在較大困難。 於如此地使用顯示裝置製造用遮罩之情形時,CD未達3 μm之微細圖案之轉印伴隨有困難,故而考慮將迄今基於半導體裝置製造之目的而開發之、用以提高解像性之各種方法亦應用於顯示裝置製造之領域。 然而,直接將上述方法應用於顯示裝置製造存在若干問題。例如,向具有高NA(數值孔徑)之高解像度之曝光裝置之轉換需要較大投資,與顯示裝置之價格之匹配性不一致。或關於曝光波長之變更(以單波長使用如ArF準分子雷射之短波長),存在難以應用於具有相對較大面積之顯示裝置之問題、製造產距易於延長之問題,除此之外於需要較大投資之方面仍不合適。 因此,若可藉由於顯示裝置製造用光罩所具備之轉印用圖案上尋找方法而提高微細圖案之轉印性,則意義重大。 作為與其相關聯之技術文獻,例如存在日本專利特開2014-211501號公報(專利文獻1)。 於上述專利文獻1中記載有相位偏移光罩基底,其特徵在於:該相位偏移光罩基底係用以製造俯視時遮光層上所形成之遮光圖案之線寬設定為較相位偏移層上所形成之相位偏移圖案之線寬窄之相位偏移光罩,且具備:透明基板;相位偏移層,其形成於該透明基板之表面,以Cr為主成分;蝕刻終止膜(蝕刻阻止膜),其形成於遠離上述透明基板側之上述相位偏移層表面,以選自Ni、Co、Fe、Ti、Si、Al、Nb、Mo、W及Hf之至少一種金屬為主成分;及遮光層,其形成於遠離上述相位偏移層側之上述蝕刻終止膜上,以Cr為主成分;藉由設定上述相位偏移層之蝕刻速率之、上述透明基板側與上述蝕刻終止膜側之比,控制蝕刻處理時間,而將俯視時側面之寬度尺寸相對於上述相位偏移層之厚度尺寸之比設定於特定範圍。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2014-211501號公報Currently, the liquid crystal display device employs a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. By adopting such a method, the liquid crystal display device is bright and power-saving, and is expected to improve the display performance of high-definition, high-speed display, and wide viewing angle. For example, in the liquid crystal display device to which the above-described methods are applied, a transparent conductive film formed in a line and gap pattern is applied to the pixel electrode, and in order to improve the display performance of the display device, further miniaturization of such a pattern is strongly desired. For example, it is preferable to reduce the distance P between the line and the gap pattern (total of the line width L and the gap width S) from 6 μm to 5 μm, and further from 5 μm to 4 μm. In this case, in most cases, at least one of the line width L and the gap width S is less than 3 μm. For example, it is not uncommon for L<3 μm, or L≦2 μm, or S<3 μm, or S≦2 μm. On the other hand, a thin film transistor (TFT) used in a liquid crystal display device or an EL (electroluminescence) display device has a configuration in which a plurality of patterns constituting a TFT are formed. The contact hole of the passivation layer (insulating layer) penetrates through the insulating layer and is conducted to the connection portion on the lower layer side thereof. At this time, if the pattern of the upper layer side and the lower layer side is not accurately positioned and the shape of the contact hole is not surely formed, the correct operation of the display device cannot be ensured. Further, here, it is also necessary to improve the display performance and the high integration of the device pattern, and to achieve a miniaturization of the pattern. That is, it is necessary to make the diameter of the hole pattern also lower than 3 μm. For example, a hole pattern having a diameter of 2.5 μm or less and further a diameter of 2.0 μm or less is required, and it is expected that a pattern having a diameter of 1.5 μm or less smaller than 2.0 μm is expected to be formed in the near future. In view of such a background, the demand for a photomask for manufacturing a display device which can cope with the minimization of line and gap patterns or contact holes continues to be high. In the field of manufacturing photomasks such as LSI (Large-Scale Integration), an optical system and a phase using a high NA (Numerical Aperture) (for example, 0.2 or more) have been developed in order to obtain resolution. The phase shifting effect of the offset effect. The phase shift mask can be used with a single wavelength short wavelength source (KrF or ArF excimer laser, etc.). Thereby, it is possible to cope with the high integration of various components and the like and the subsequent miniaturization of the reticle pattern. On the other hand, in the field of lithography for manufacturing a display device, generally, the above-described method is not used to improve the resolution or the depth of focus. The reason for this is that, in the display device, the degree of integration and fineness of the desired pattern are inferior to those in the semiconductor manufacturing field. In fact, an optical system or a light source mounted in an exposure apparatus for manufacturing a display device (generally known as an LCD (Liquid Crystal Display) exposure apparatus or a liquid crystal exposure apparatus) is also used for semiconductor manufacturing. The optical system or the light source is different, and the production efficiency (for example, increasing the wavelength region of the light source to obtain a larger amount of illumination light, shortening the production distance, etc.) is more important than the resolution and depth of focus. When the transfer pattern of the photomask is made fine, the step of accurately transferring the transfer pattern to the transfer target (the film to be etched, which is also referred to as a workpiece) is difficult to carry out. The reason for this is that the above-described exposure apparatus for the transfer step of the display device manufacturing in actual production has a resolution limit of about 3 μm, but in the transfer pattern required for the display device, the above-mentioned CD (Critical Dimension: line) is required. Wide) is close to or below 3 μm. Further, since the mask for manufacturing a display device has a larger area than the mask for semiconductor manufacturing, it is difficult to uniformly transfer the surface of the transfer pattern having a CD of less than 3 μm in actual production. . When the mask for manufacturing a display device is used as described above, it is difficult to transfer a fine pattern having a CD of less than 3 μm, and thus it is considered to improve the resolution by the purpose of manufacturing the semiconductor device up to now. Various methods are also applied to the field of display device manufacturing. However, there are several problems in directly applying the above method to the manufacture of a display device. For example, conversion to an exposure apparatus having a high resolution of high NA (numerical aperture) requires a large investment, and the matching with the price of the display device is inconsistent. Or regarding the change of the exposure wavelength (using a short wavelength such as an ArF excimer laser at a single wavelength), there is a problem that it is difficult to apply to a display device having a relatively large area, and the manufacturing yield is prone to be prolonged, and The need for a larger investment is still not appropriate. Therefore, it is of great significance to improve the transferability of the fine pattern by the method for finding a pattern for transfer which is provided in the photomask for manufacturing a display device. For example, Japanese Laid-Open Patent Publication No. 2014-211501 (Patent Document 1) is known. Patent Document 1 discloses a phase shift mask substrate characterized in that the phase shift mask base is used to manufacture a light-shielding pattern formed on a light-shielding layer in a plan view, and a line width is set to be a phase shift layer. a phase shift mask having a narrow line width of the phase shift pattern formed thereon, and comprising: a transparent substrate; a phase shift layer formed on the surface of the transparent substrate, with Cr as a main component; and an etch stop film (etching blocking a film) formed on a surface of the phase shift layer away from the transparent substrate side, and having at least one metal selected from the group consisting of Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf as a main component; a light shielding layer formed on the etching stopper film away from the phase shift layer side, wherein Cr is a main component; and the transparent substrate side and the etching stopper film side are set by setting an etching rate of the phase shift layer The ratio of the width dimension of the side surface in the plan view to the thickness dimension of the phase shift layer is set to a specific range. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-211501
[發明所欲解決之問題] 然而,於上述專利文獻1中所記載之技術中,存在以下問題。 蝕刻終止膜(蝕刻阻止膜)之材料或組成、進而相位偏移膜與遮光膜之蝕刻速率未經充分調整,圖案之面內均一性因相位偏移圖案與遮光圖案之粗密度而不足。即,於相位偏移光罩存在粗密圖案之情形時,藉由專利文獻1中所記載之材料只能有所限度地按照設計將圖案圖案化。 又,於對包含金屬矽化物之蝕刻終止膜進行蝕刻時,通常使用含有氟化氫銨之蝕刻液。然而,該蝕刻液會對玻璃基板造成不小損傷,而產生以下等問題:於蝕刻時間較長之情形時,因玻璃基板遭到腐蝕而發生相位差之變化;於相位偏移光罩之透光部存在龜裂之情形時,龜裂推進而使透光部產生凹缺陷。 進而,於如相位偏移光罩般之高精度遮罩中,亦嚴格要求缺陷品質,會自缺陷品質之方面考慮而以中途停用蝕刻液之方式進行蝕刻,但於該情形時亦存在以下問題:若蝕刻時間較長,則蝕刻液之消耗量會非常多。 鑒於以上方面,本發明之第一目的在於提供一種相位偏移光罩基底,其係用以獲得可抑制製作相位偏移光罩時之蝕刻液之消耗量,具有微細且高精度之圖案,不會產生凹缺陷之相位偏移光罩。 本發明之第二目的在於提供一種相位偏移光罩,其可抑制製作相位偏移光罩時之蝕刻液之消耗量,具有微細且高精度之圖案,不會產生凹缺陷。 [解決問題之技術手段] 基於以上內容,為了達成上述目的,本發明具有以下構成。 (構成1) 一種相位偏移光罩基底,其特徵在於:其係相位偏移光罩之母版,該相位偏移光罩係於透明基板上藉由濕式蝕刻將相位偏移膜、蝕刻阻止膜、遮光膜分別圖案化,藉此形成包含遮光部、相位偏移部、透光部之轉印圖案而成,且該相位偏移光罩係藉由使透過上述相位偏移部之光之相位與透過上述透光部之光之相位不同,而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度;且 上述相位偏移光罩基底於上述透明基板上依序形成有相位偏移膜、蝕刻阻止膜、遮光膜, 上述相位偏移膜包括含有鉻與選自氧、氮、碳、氟中之至少一者之鉻化合物, 上述蝕刻阻止膜包括含有金屬與矽之金屬矽化物, 上述相位偏移膜與上述遮光膜係能夠藉由同一種蝕刻液A進行蝕刻之材料,且以上述遮光膜面對上述蝕刻液A之濕式蝕刻速度快於上述相位偏移膜面對上述蝕刻液A之濕式蝕刻速度之方式進行調整, 上述蝕刻阻止膜係對上述遮光膜之蝕刻液A具有抗蝕性之材料,且以直至上述蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間為15分鐘以下之方式調整上述蝕刻阻止膜之膜厚、材料、組成比。 (構成2) 如構成1之相位偏移光罩基底,其中上述蝕刻阻止膜係對上述遮光膜之蝕刻液A具有抗蝕性之材料,且以直至上述蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間為10分鐘以下之方式調整上述蝕刻阻止膜之膜厚、材料、組成比。 (構成3) 如構成1或2之相位偏移光罩基底,其中上述蝕刻阻止膜之膜厚為5 nm以上且75 nm以下。 (構成4) 如構成1至3中任一項之相位偏移光罩基底,其中上述蝕刻阻止膜中之上述金屬與上述矽之比率為金屬:矽=1:2以上且1:9以下。 (構成5) 如構成1至4中任一項之相位偏移光罩基底,其中上述蝕刻阻止膜係金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、或金屬矽化物之碳氮氧化物,且上述氮之含量為20原子%以上且50原子%以下。 (構成6) 如構成5之相位偏移光罩基底,其中上述蝕刻阻止膜中之上述氮之含量為25原子%以上且45原子%以下。 (構成7) 如構成1至6中任一項之相位偏移光罩基底,其中上述遮光膜面對上述蝕刻液A之濕式蝕刻速度為上述相位偏移膜面對上述蝕刻液A之濕式蝕刻速度之1.5~5倍。 (構成8) 如構成1至7中任一項之相位偏移光罩基底,其中直至上述蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間為10秒以上。。 (構成9) 如構成1至8中任一項之相位偏移光罩基底,其中上述相位偏移光罩基底之一邊之長度為300 mm以上。 (構成10) 一種相位偏移光罩之製造方法,其特徵在於具有以下步驟: 於如構成1至9中任一項之相位偏移光罩基底上形成抗蝕膜; 對上述抗蝕膜進行特定圖案之繪圖、顯影處理,而形成抗蝕圖案; 將上述抗蝕圖案作為遮罩,藉由上述蝕刻液A對上述遮光膜進行濕式蝕刻,而形成臨時遮光膜圖案; 將上述臨時遮光膜圖案作為遮罩,藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻,而形成臨時蝕刻阻止膜圖案; 將上述臨時蝕刻阻止膜圖案作為遮罩,藉由上述蝕刻液A對上述相位偏移膜進行濕式蝕刻,而形成基於相位偏移膜圖案之相位偏移部,並藉由對上述臨時遮光膜圖案進行側面蝕刻而形成遮光膜圖案; 將上述遮光膜圖案作為遮罩,藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻,而形成蝕刻阻止膜圖案,於上述相位偏移膜圖案上形成基於上述蝕刻阻止膜圖案與上述遮光膜圖案之遮光部;及 去除上述抗蝕圖案。 (構成11) 如構成10之相位偏移光罩之製造方法,其中上述蝕刻阻止膜圖案之形成時間為10秒以上且15分鐘以下。 (構成12) 如構成11之相位偏移光罩之製造方法,其中形成上述蝕刻阻止膜圖案時所使用之蝕刻液B係包含過氧化氫、氟化銨、以及選自磷酸、硫酸及硝酸中至少一者之氧化劑的蝕刻液。 (構成13) 如構成10之相位偏移光罩之製造方法其中上述蝕刻阻止膜圖案之形成時間為10秒以上且10分鐘以下。 (構成14) 如構成13之相位偏移光罩之製造方法,其中形成上述蝕刻阻止膜圖案時所使用之蝕刻液B係包含選自氫氟酸、氟矽酸、及氟化氫銨中至少一者之氟化合物與選自過氧化氫、硝酸、及硫酸中至少一者之氧化劑的蝕刻液。 (構成15) 如構成10至14中任一項之相位偏移光罩之製造方法,其中上述相位偏移光罩係以上述遮光膜圖案與上述相位偏移膜圖案之中心重合之方式製造。 (構成16) 如構成10至15中任一項之相位偏移光罩之製造方法其中上述轉印圖案包含線與間隙圖案,上述線與間隙圖案之線圖案具有固定寬度之上述遮光部、及與上述固定寬度之遮光部之邊緣鄰接之固定寬度之上述相位偏移部。 (構成17) 如構成10至15中任一項記載之相位偏移光罩之製造方法,其中上述轉印圖案包含孔圖案,上述孔圖案具有特定直徑之上述透光部、包圍上述透光部之固定寬度之上述相位偏移部、及包圍上述相位偏移部之上述遮光部。 (構成18) 一種顯示裝置之製造方法,其特徵在於包括以下步驟: 準備藉由如構成10至17中任一項之相位偏移光罩之製造方法而製造之相位偏移光罩;及 使用照射曝光之光之顯示裝置製造用曝光裝置,曝光上述相位偏移光罩之上述轉印圖案,而將上述轉印圖案轉印於被轉印體上。 [發明之效果] 根據本發明,可獲得一種相位偏移光罩基底,其係用以獲得可抑制製作相位偏移光罩時之蝕刻液之消耗量,具有微細且高精度之圖案,不會產生凹缺陷之相位偏移光罩。 又,根據本發明,可獲得一種相位偏移光罩,其可抑制製作相位偏移光罩時之蝕刻液之消耗量,具有微細且高精度之圖案,不會產生凹缺陷。[Problems to be Solved by the Invention] However, in the technique described in Patent Document 1, there are the following problems. The material or composition of the etching stopper film (etching stopper film), and further the etching rate of the phase shift film and the light shielding film are not sufficiently adjusted, and the in-plane uniformity of the pattern is insufficient due to the coarseness of the phase shift pattern and the light shielding pattern. That is, in the case where the phase shift mask has a coarse pattern, the material described in Patent Document 1 can be patterned in a limited manner according to the design. Further, when etching an etching stopper film containing a metal halide, an etching solution containing ammonium hydrogen fluoride is usually used. However, the etching solution causes a small damage to the glass substrate, and causes problems such as a change in phase difference due to corrosion of the glass substrate in the case where the etching time is long; and the phase shift mask is transparent. When there is a crack in the light portion, the crack propagates to cause a concave defect in the light transmitting portion. Further, in the high-precision mask such as the phase shift mask, the defect quality is strictly required, and the etching liquid is etched in the middle of the defect quality, but in this case, the following is also present. Problem: If the etching time is long, the etching liquid consumption will be very large. In view of the above, a first object of the present invention is to provide a phase shift mask substrate which is used to obtain an etchant which can suppress the consumption of a phase shift mask, and has a fine and high precision pattern, A phase shift mask that produces a concave defect. A second object of the present invention is to provide a phase shift mask which can suppress the consumption of an etching liquid when a phase shift mask is produced, and has a fine and highly precise pattern without causing concave defects. [Technical means for solving the problem] Based on the above, the present invention has the following configuration in order to achieve the above object. (Configuration 1) A phase shift mask substrate characterized in that it is a master of a phase shift mask, the phase shift mask is attached to a transparent substrate, and a phase shift film is etched by wet etching. The blocking film and the light shielding film are respectively patterned, thereby forming a transfer pattern including a light shielding portion, a phase shift portion, and a light transmitting portion, and the phase shift mask is made to transmit light passing through the phase shift portion The phase is different from the phase of the light transmitted through the light transmitting portion, and the light in the vicinity of the boundary portion between the phase shifting portion and the light transmitting portion cancels each other to improve the contrast of the boundary portion; and the phase shift mask base a phase shift film, an etching stopper film, and a light shielding film are sequentially formed on the transparent substrate, and the phase shift film includes a chromium compound containing chromium and at least one selected from the group consisting of oxygen, nitrogen, carbon, and fluorine. The blocking film includes a metal telluride containing a metal and a germanium, and the phase shifting film and the light shielding film are materials which can be etched by the same etching liquid A, and the wet etching is performed by the light shielding film facing the etching liquid A. The speed is faster than the phase shifting film facing the wet etching rate of the etching liquid A, and the etching stopper film is made of a material resistant to the etching liquid A of the light shielding film, and is blocked until the etching is performed. The film thickness, material, and composition ratio of the etching stopper film are adjusted so that the time required for the film to be peeled off by the etching liquid B which can be etched is 15 minutes or less. (Configuration 2) The phase shift mask substrate of the first aspect, wherein the etching stopper film is a material having a resist property to the etching liquid A of the light shielding film, and the etching stopper film can be etched by the etching stopper film The film thickness, material, and composition ratio of the etching stopper film were adjusted so that the time required for the etching liquid B to be peeled off was 10 minutes or less. (Configuration 3) The phase shift mask substrate of the first or second aspect, wherein the etching stopper film has a film thickness of 5 nm or more and 75 nm or less. (Aspect 4) The phase shift mask substrate according to any one of 1 to 3, wherein a ratio of the metal to the germanium in the etching stopper film is metal: 矽 = 1:2 or more and 1:9 or less. (Claim 5) The phase shift mask substrate according to any one of 1 to 4, wherein the etching stopper film is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, Or a oxycarbonitride of a metal telluride, and the content of the above nitrogen is 20 atom% or more and 50 atom% or less. (Configuration 6) The phase shift mask substrate of the fifth aspect, wherein the content of the nitrogen in the etching stopper film is 25 atom% or more and 45 atom% or less. (Structure 7) The phase shift mask substrate according to any one of 1 to 6, wherein a wet etching speed of the light shielding film facing the etching liquid A is wet of the phase shift film facing the etching liquid A The etching speed is 1.5 to 5 times. (Aspect 8) The phase shift mask substrate according to any one of 1 to 7, wherein a time required for the etching stop film to be peeled off by the etching liquid B which can be etched is 10 seconds or longer. . (Aspect 9) The phase shift mask substrate according to any one of 1 to 8, wherein a length of one side of the phase shift mask base is 300 mm or more. (Configuration 10) A method of manufacturing a phase shift mask, comprising the steps of: forming a resist film on a phase shift mask substrate according to any one of Embodiments 1 to 9; Forming a resist pattern by drawing and developing a specific pattern; using the resist pattern as a mask, wet etching the light-shielding film by the etching liquid A to form a temporary light-shielding film pattern; a pattern is used as a mask, and the etching stopper film is wet-etched by the etching liquid B to form a temporary etching stopper film pattern; and the temporary etching stopper film pattern is used as a mask, and the phase is biased by the etching liquid A Transferring the film to perform wet etching to form a phase shifting portion based on the phase shift film pattern, and forming a light shielding film pattern by side etching the temporary light shielding film pattern; using the light shielding film pattern as a mask The etching solution B wet-etches the etching stopper film to form an etching stopper film pattern, and forms the etching resistance on the phase shift film pattern. The light shielding film pattern and the light shielding film pattern portion; and removing the resist pattern. (Configuration 11) The method of manufacturing a phase shift mask according to the configuration 10, wherein the formation time of the etching stopper film pattern is 10 seconds or longer and 15 minutes or shorter. (Configuration 12) The method for manufacturing a phase shift mask according to the configuration 11, wherein the etching liquid B used in forming the etching stopper film pattern contains hydrogen peroxide, ammonium fluoride, and selected from phosphoric acid, sulfuric acid, and nitric acid. An etchant of at least one of the oxidizing agents. (Configuration 13) The method of manufacturing a phase shift mask of the configuration 10, wherein the formation time of the etching stopper film pattern is 10 seconds or longer and 10 minutes or shorter. (Configuration 14) The method of manufacturing a phase shift mask according to the configuration 13, wherein the etching liquid B used in forming the etching stopper film pattern contains at least one selected from the group consisting of hydrofluoric acid, fluoroantimonic acid, and ammonium hydrogen fluoride. An etching solution of the fluorine compound and an oxidizing agent selected from at least one of hydrogen peroxide, nitric acid, and sulfuric acid. The method of manufacturing a phase shift mask according to any one of 10 to 14, wherein the phase shift mask is manufactured such that the light shielding film pattern overlaps with a center of the phase shift film pattern. In a method of manufacturing a phase shift mask according to any one of 10 to 15, wherein the transfer pattern includes a line and a gap pattern, the line pattern of the line and gap pattern has a light-shielding portion having a fixed width, and The phase shifting portion having a fixed width adjacent to an edge of the light-shielding portion of the fixed width. In a method of manufacturing a phase shift mask according to any one of 10 to 15, wherein the transfer pattern includes a hole pattern, the hole pattern has the light-transmitting portion having a specific diameter, and surrounds the light-transmitting portion. The phase shifting portion having a fixed width and the light blocking portion surrounding the phase shifting portion. (Configuration 18) A method of manufacturing a display device, comprising the steps of: preparing a phase shift mask manufactured by the method of manufacturing a phase shift mask according to any one of 10 to 17; The exposure device for manufacturing a display device for exposing the exposed light exposes the transfer pattern of the phase shift mask, and transfers the transfer pattern onto the transfer target. [Effects of the Invention] According to the present invention, it is possible to obtain a phase shift mask substrate which is used to obtain a pattern which can suppress the consumption of an etching liquid when a phase shift mask is produced, and which has a fine and high-precision pattern and does not A phase shift mask that produces a concave defect. Moreover, according to the present invention, it is possible to obtain a phase shift mask which can suppress the consumption of the etching liquid when the phase shift mask is formed, and has a fine and highly precise pattern without causing concave defects.
以下,一面參照圖式一面具體地說明本發明之實施形態。再者,以下之實施形態係將本發明具體化時之一形態,而並非將本發明限定於其範圍內者。圖中,存在對相同或等效之部分標註相同符號並簡化甚至省略其說明之情形。 (本發明之實施形態) 首先,對本發明之實施形態之相位偏移光罩基底進行說明。 <相位偏移光罩基底> 本發明之實施形態之相位偏移光罩基底之特徵在於: 其係相位偏移光罩之母版,該相位偏移光罩係於透明基板上藉由濕式蝕刻將相位偏移膜、蝕刻阻止膜、遮光膜分別圖案化,藉此形成包含遮光部、相位偏移部、透光部之轉印圖案而成,且該相位偏移光罩係藉由使透過上述相位偏移部之光之相位與透過上述透光部之光之相位不同,而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度;且 上述相位偏移光罩基底於上述透明基板上依序形成有相位偏移膜、蝕刻阻止膜、遮光膜, 上述相位偏移膜包括含有鉻與選自氧、氮、碳、氟中之至少一者之鉻化合物, 上述蝕刻阻止膜包括含有金屬與矽之金屬矽化物, 上述相位偏移膜與上述遮光膜係能夠藉由同一種蝕刻液A進行蝕刻之材料,且以上述遮光膜面對上述蝕刻液A之濕式蝕刻速度快於上述相位偏移膜面對上述蝕刻液A之濕式蝕刻速度之方式進行調整, 上述蝕刻阻止膜係對上述遮光膜之蝕刻液A具有抗蝕性之材料,且以直至上述蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間為15分鐘以下之方式調整上述蝕刻阻擋膜之膜厚、材料、組成比。 參照圖1,對本發明之實施形態之相位偏移光罩基底之具體構成進行說明。 如圖1所示,本發明之實施形態之相位偏移光罩基底10係於透明基板11上依序形成相位偏移膜12、蝕刻阻止膜13、遮光膜14而成。 而且,可藉由準備以上述方式形成之相位偏移光罩基底10,並將相位偏移膜12、蝕刻阻止膜13、遮光膜14圖案化而製造相位偏移光罩。 其次,對本發明之實施形態之相位偏移光罩進行說明。 <相位偏移光罩> 藉由使透過相位偏移部之光之相位與透過透光部之光之相位不同,而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度的相位偏移光罩主要多用於半導體製造領域。已知該等相位偏移光罩係使用對曝光之光(例如,KrF或ArF之準分子雷射)之透過率為5~10%左右且使該曝光之光之相位大致偏移180度之相位偏移膜。 其中,該領域中所使用之相位偏移光罩通常係應用乾式蝕刻而製造,故而不存在因為採用上述濕式蝕刻而產生之問題點凸顯化之情形。然而,於顯示裝置製造用之相位偏移光罩中,如上所述,透明基板之尺寸相對大型(使用一邊為300 mm以上之矩形形狀之基板),且其尺寸之種類多種多樣,故而相較於使用乾式蝕刻,應用濕式蝕刻更為有利。顯示裝置製造用之相位偏移光罩中所使用之矩形形狀之透明基板之尺寸例如可使用330 mm×450 mm至1620 mm×1780 mm。 本發明之相位偏移光罩(光罩,photomask)係於透明基板上藉由濕式蝕刻將相位偏移膜、蝕刻阻止膜、遮光膜分別圖案化,藉此形成包含遮光部、相位偏移部、透光部之轉印圖案而成的相位偏移光罩,且係藉由使透過上述相位偏移部之光之相位與透過上述透光部之光之相位不同,而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度的相位偏移光罩。 此處,參照圖2對本發明之一實施態樣之相位偏移光罩進行說明。其中,圖2係形成有線與間隙圖案之第1實施態樣之相位偏移光罩之剖視圖(下側)及對應之俯視圖(上側)。 相位偏移光罩10a可藉由準備於圖1所示之透明基板11上依序形成相位偏移膜12、蝕刻阻止膜13、遮光膜14而成之相位偏移光罩基底10,並將相位偏移膜12、蝕刻阻止膜13、遮光膜14圖案化而製造。 但亦可於不妨礙本發明之效果之範圍內,於該等膜之間、或任一膜與透明基板11之間介置其他膜。 圖2之上側之圖係相位偏移光罩10a之俯視圖,於自上方觀察相位偏移光罩10a之情形時,可看到圖案化後之遮光膜14(即遮光膜圖案14a)之部分構成遮光部18,可看到圖案化後之相位偏移膜12(即相位偏移膜圖案12a)之部分構成相位偏移部16,未被相位偏移膜12、蝕刻阻止膜13及遮光膜14中任一者覆蓋而露出透明基板11之部分構成透光部17。該透光部17與上述相位偏移部16具有邊界部(鄰接部分)。 於使用本發明之相位偏移光罩進行顯示裝置之圖案形成之情形時,作為轉印特性良好之線與間隙圖案,例如較佳為4(μm)≦間距P<6(μm)且線寬L≧1.5(μm),間隙寬S≦3.5(μm)。於重視圖案轉印時之對比度之高度之情形時,於間距P<6(μm)之微細之線與間隙圖案中,較佳為線寬L≧間隙寬S,包含與遮光部之邊緣鄰接之固定寬度之相位偏移部之邊緣寬度(rim width)R較佳為R≧0.8(μm)。再者,於線與間隙圖案中,通常設置有包含與遮光部之兩側鄰接之固定寬度之相位偏移部之邊緣寬度。該情形時之上述邊緣寬度R較理想亦為上述範圍R≧0.8(μm)。 此處,遮光部18係透明基板11上之至少形成有遮光膜圖案14a之部分,其對曝光之光之透過率實質上為零。相位偏移部16係於透明基板11上形成具有特定透過率(例如6%(i線:波長365 nm))之相位偏移膜圖案12a而成之部分,與透光部17之相位差為特定相位差(例如180度(i線:波長365 nm))。 如此,本發明之相位偏移光罩10a具有轉印用圖案,該轉印用圖案係於透明基板11上基於特定之圖案設計藉由濕式蝕刻將相位偏移膜12、蝕刻阻止膜13、遮光膜14分別圖案化而形成。 於此種構成之下,透過相位偏移部16之曝光之光使其相位相對於透過透光部17之曝光之光大致偏移180度,從而與透過透光部17後之曝光之光於鄰接部分相互干涉。藉此該部分之光之對比度提高,曝光之光之強度曲線之邊緣形狀變得更加銳利。因此,本發明之相位偏移光罩10a亦可應對近年來所要求之顯示裝置製造中之微細圖案。 此處,相位偏移光罩基底10、及相位偏移光罩10a之構成可設定為如下。 (透明基板11) 透明基板11之材料只要係對所使用之曝光之光具有透光性之材料便不加以特別限制。例如可列舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃。 (相位偏移膜12) 本發明中之相位偏移膜12因透過曝光之光之一部分,而可說成是半透光性之膜。又,具有使曝光之光之相位偏移特定量之作用。 該相位偏移膜12包括含有鉻與選自氧、氮、碳、氟中之至少一者之鉻化合物。 本發明中之相位偏移膜12包括含有鉻之材料。例如,較佳為含有鉻氧化物(CrOx)、鉻氮化物(CrNx)、鉻碳化物(CrCx)、鉻氮氧化物(CrOxNy)、鉻碳氮化物(CrCxNy)、鉻碳氧化物(CrOxCy)、鉻碳氮氧化物(CrOxNyCz)、鉻氟化物(CrFx)中任一者。相位偏移膜12之膜厚較佳為80~180 nm。 於上述相位偏移膜12之濕式蝕刻中可使用公知之蝕刻液。例如,可使用硝酸鈰銨與過氯酸之混合水溶液。 於相位偏移光罩10a中,相位偏移膜12對曝光之光之透過率可為1~50%、1.5~30%、2~15%,更佳可為3~8%。此處,曝光之光可使用為LCD曝光裝置通常所採用之光源且包含i線、h線、g線中任一者之光,更佳為使用包含該等全部之光。作為曝光之光之透過率,將上述中任一者作為代表波長,而定義透過率及相位差(或相位偏移量)。 又,於相位偏移光罩10a中,將相位偏移膜12所具有之曝光之光(例如將i線作為代表波長)之相位偏移量設為大致180度。此處,所謂大致180度係指可為160度~200度,較佳可為170~190度。 又,就上述相位偏移膜12而言,波長365 nm(i線)至436 nm(g線)範圍內之光之相位偏移量之變動幅度(波長365 nm至436 nm之、於相位偏移膜12之最大相位偏移量與最小相位偏移量之差)較佳為40度以內,更佳為30度以內。藉由使上述變動幅度處於此種範圍內,可充分獲得使代表波長之相位偏移量為大致180度之效果。 (蝕刻阻止膜13) 蝕刻阻止膜13係包括含有金屬與矽之金屬矽化物,且對下述遮光膜之蝕刻液A(於遮光膜為包含Cr之鉻化合物之情形時,該蝕刻液A例如為硝酸鈰銨與過氯酸之混合水溶液)具有抗蝕性之材料,且以直至蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B(例如,氟化氫銨與過氧化氫之混合水溶液、或過氧化氫、氟化銨及磷酸之混合水溶液)而剝離所需之時間為15分鐘以下、較佳為10分鐘以下之方式選定膜厚、材料、組成比。以下對蝕刻阻止膜13之膜厚、材料、組成比進行說明。 蝕刻阻止膜13之膜厚較佳為5 nm以上且75 nm以下。 為了發揮作為蝕刻阻止膜13之功能,其膜厚較佳為5 nm以上。若蝕刻阻止膜13之膜厚過厚,則藉由蝕刻液B剝離蝕刻阻止膜13時,蝕刻液B與透明基板(玻璃基板)11之接觸時間較長,會發生因玻璃基板遭到腐蝕而導致之透過率降低、或因龜裂而導致之凹缺陷。又,於自缺陷品質之方面考慮而以中途停用蝕刻液之方式進行蝕刻製程之情形時,一旦膜厚較厚則蝕刻液B之消耗量便會非常多。就該等方面而言蝕刻阻止膜13之膜厚較佳為75 nm以下。 此處,蝕刻阻止膜13係含有金屬與矽之金屬矽化物(金屬矽化物系材料),其中尤為金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、或金屬矽化物之碳氮氧化物,且氮之含量較佳為20原子%以上且50原子%以下。蝕刻阻止膜13中之氮之含量更佳為25原子%以上且45原子%以下。 構成蝕刻阻止膜13之金屬矽化物系材料只要係包含金屬與矽者便不加以特別限制。為了使藉由濕式蝕刻而形成之蝕刻阻止膜圖案之剖面形狀良好,進而使將蝕刻阻止膜圖案作為遮罩藉由濕式蝕刻而形成之相位偏移膜圖案之剖面形狀良好,金屬與矽之比率較佳為金屬:矽=1:2以上且1:9以下。 若金屬與矽之比率係比起1:2金屬之含量更多(金屬:矽之比率未達1:2),則於形成具有粗圖案與密圖案之圖案時,難以精度較佳地形成圖案。又,若金屬與矽之比率係比起1:9矽之含量更多(金屬:矽之比率超過1:9),則蝕刻速度變慢,故而會發生與上述相同之不良狀況。 尤佳地,構成蝕刻阻止膜13之金屬矽化物系材料中之金屬與矽之比率較理想為金屬:矽=1:2以上且1:8以下。作為金屬,可列舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)、鋯(Zr)等過渡金屬。 作為構成蝕刻阻止膜13之金屬矽化物系材料,例如可列舉金屬矽化物、金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之碳化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、金屬矽化物之碳氧化物、或金屬矽化物之碳氮氧化物。具體而言,可列舉:鉬矽化物(MoSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物;鉭矽化物(TaSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物;鎢矽化物(WSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物;鈦矽化物(TiSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物;鋯矽化物(ZrSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物。 就與相位偏移膜12之密接性之提高以及相位偏移膜12及蝕刻阻止膜13之剖面控制性之方面而言,其中尤以金屬矽化物系材料係金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物為佳。於該情形時,氮之含量較理想為25原子%以上且45原子%以下。又,為了使蝕刻阻止膜13具有反射率降低功能,較佳為進而含有氧。 對於上述蝕刻阻止膜13,以直至該蝕刻阻止膜13藉由能夠對其進行蝕刻之蝕刻液B(例如,氟化氫銨與過氧化氫之混合水溶液、或過氧化氫、氟化銨及磷酸之混合水溶液)而剝離所需之時間為10分鐘以下之方式調整、選定蝕刻阻止膜13之膜厚、材料、組成比。本發明中所使用之顯示裝置製造用之相位偏移光罩基底一般是一邊之長度為300 mm以上之較大尺寸,故而於向基板面內供給蝕刻液時容易產生蝕刻不均。若考慮到蝕刻不均,則直至上述蝕刻阻止膜13藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間較佳為10秒以上。進而較佳地,上述時間較理想為10秒以上且15分鐘以下,更理想為10秒以上且10分鐘以下。 考慮到蝕刻液B對玻璃基板所造成之損傷,於形成上述蝕刻阻止膜圖案時所使用之蝕刻液B為包含過氧化氫、氟化銨、以及選自磷酸、硫酸及硝酸中至少一者之氧化劑的蝕刻液之情形時,較佳為以直至藉由蝕刻液B而剝離所需之時間為10秒以上且20分鐘以下之方式調整上述蝕刻阻止膜13之膜厚、材料、組成比。又,就相同之觀點而言,於形成上述蝕刻阻止膜圖案時所使用之蝕刻液B為包含選自氫氟酸、氟矽酸、及氟化氫銨中至少一者之氟化合物與選自過氧化氫、硝酸、及硫酸中至少一者之氧化劑的蝕刻液之情形時,較佳為以直至藉由蝕刻液B而剝離所需之時間為10秒以上且10分鐘以下之方式調整上述蝕刻阻止膜13之膜厚、材料、組成比。 (遮光膜14) 遮光膜14較佳為於與相位偏移膜12、蝕刻阻止膜13積層之狀態下具有充分之遮光性(光學濃度(OD)為3以上)。更佳為僅以遮光膜14便具有充分之遮光性(光學濃度(OD)為3以上)。又,遮光膜14較佳為具有與蝕刻阻止膜13之蝕刻選擇性。即,較理想為蝕刻阻止膜13對能夠蝕刻遮光膜14之蝕刻液具有抗蝕性。 作為遮光膜14之材料,可較佳地使用包含Cr者。例如,除含有鉻以外,較佳為含有鉻氧化物(CrOx)、鉻氮化物(CrNx)、鉻碳化物(CrCx)、鉻氮氧化物(CrOxNy)、鉻碳氮化物(CrCxNy)、鉻碳氧化物(CrOxCy)、鉻碳氮氧化物(CrOxNyCz)中任一者。 遮光膜14亦可於其表面設置抗反射層。於該情形時,抗反射層可為鉻氧化物、鉻氮化物及鉻酸氮化物中任一者。 又,上述相位偏移膜12與上述遮光膜14為能夠藉由同一種蝕刻液(A)(例如,硝酸鈰銨與過氯酸之混合水溶液)進行蝕刻之材料,且以上述遮光膜面對上述蝕刻液(A)之濕式蝕刻速度快於上述相位偏移膜面對蝕刻液(A)之濕式蝕刻速度之方式,藉由添加於上述相位偏移膜12或上述遮光膜14中之氧、氮、碳、氟之含量而進行調整。 遮光膜14之膜厚可為50~200 nm,更佳為80~150 nm,進而更佳為90~130 nm。 作為遮光膜14之蝕刻液並不加以特別限制,可使用先前公知者,於遮光膜14係利用包含鉻之材料而形成之情形時,對遮光膜14所使用之蝕刻液與上述相位偏移膜12中所述者相同。 相位偏移光罩10a可使露出於表面之面全部為鉻系之膜,故而耐化學品性較高,較為有利。作為成膜方法,相位偏移光罩10a之各構成膜均可採用濺鍍法、離子鍍覆法、或蒸鍍法等,就提高2個膜之界面密接性之方面而言較佳為濺鍍法。 如此,本發明之相位偏移光罩10a可較佳地應用於例如包含形成顯示裝置之像素電極等之線與間隙圖案作為轉印圖案之光罩。 又,如圖3所示,轉印圖案亦可應用於包含形成接觸孔之孔圖案者。作為孔圖案,包含具有固定之規則性(間距)且複數個接觸孔排列者。 此處,圖3係本發明之孔圖案用之相位偏移光罩10b之剖視圖(下側)及對應之俯視圖(上側)。 如圖3所示,孔圖案具有特定孔徑之透光部17、包圍透光部17之固定寬度之相位偏移部16、及包圍上述相位偏移部16之遮光部18。 此處,透光部17之孔徑(於正方形之情形時為1邊之長度,於長方形之情形時為短邊之長度,於圓形之情形時為直徑)可為1.5~5(μm),相位偏移部16之寬度(邊緣寬度R)可為0.3(μm)≦R≦1.5(μm)。 <相位偏移光罩之製造方法> 本發明之相位偏移光罩之製造方法具有以下步驟: 於上文所說明之本發明之實施形態之上述相位偏移光罩基底上形成抗蝕膜; 對上述抗蝕膜進行特定圖案之繪圖、顯影處理,而形成抗蝕圖案; 將上述抗蝕圖案作為遮罩,藉由上述蝕刻液A對上述遮光膜進行濕式蝕刻,而形成臨時遮光膜圖案; 將上述臨時遮光膜圖案作為遮罩,藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻,而形成臨時蝕刻阻止膜圖案; 將上述臨時蝕刻阻止膜圖案作為遮罩,藉由上述蝕刻液A對上述相位偏移膜進行濕式蝕刻,而形成基於相位偏移膜圖案之相位偏移部,並藉由對上述臨時遮光膜圖案進行側面蝕刻而形成遮光膜圖案; 將上述遮光膜圖案作為遮罩,藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻,而形成蝕刻阻止膜圖案,於上述相位偏移膜圖案上形成基於上述蝕刻阻止膜圖案與上述遮光膜圖案之遮光部;及 去除上述抗蝕圖案。 以此方式操作,製造於透明基板上具備具有相位偏移部、遮光部、透光部之轉印圖案之相位偏移光罩。 而且,於相位偏移膜12、蝕刻阻止膜13、及遮光膜14之圖案化中可包括以下步驟。 此處,首先參照圖4對作為參考例之相位偏移光罩10c之製造方法進行說明,以使本發明之相位偏移光罩10a、10b之製造方法之特徵更加明確。 <參考例之相位偏移光罩10c之製造方法> 參考例之相位偏移光罩10c之製造方法係於製作該相位偏移光罩10c時兩次形成抗蝕膜之相位偏移光罩之製造方法。 圖4係表示參考例之態樣之相位偏移光罩10c的製造方法之例之圖。 首先,準備圖1所示之相位偏移光罩基底10,於相位偏移光罩基底10之遮光膜14上形成第1光阻膜15(圖4(a))。 其後,藉由對第1光阻膜15進行繪圖及顯影而形成第1抗蝕圖案15a,並藉由將第1抗蝕圖案15a作為遮罩,利用蝕刻液A對遮光膜14進行濕式蝕刻,而形成遮光膜圖案14a(圖4(b))。 其次,剝離第1抗蝕圖案15a(圖4(c))。 其次,於形成有遮光膜圖案14a之透明基板11整面形成第2光阻膜19(圖4(d)), 並藉由對第2光阻膜19進行繪圖及顯影而形成第2抗蝕圖案19a(圖4(e))。 其次,將第2抗蝕圖案19a作為遮罩,利用蝕刻液B對蝕刻阻止膜13進行濕式蝕刻,而形成蝕刻阻止膜圖案13a(圖4(f))。 其次,將所獲得之蝕刻阻止膜圖案13a作為遮罩,利用蝕刻液A對相位偏移膜12進行濕式蝕刻,而形成相位偏移膜圖案12a,其後,剝離第2抗蝕圖案19a(圖4(g))。 最後,將遮光膜圖案14a作為遮罩,利用蝕刻液B對蝕刻阻止膜圖案13a進行濕式蝕刻,則相位偏移光罩10c完成((圖4(h))。 然而,於上述相位偏移光罩10c之參考製法中,如圖4所示,兩次形成光阻膜(第1光阻膜15、第2光阻膜19),並對第1光阻膜15及第2光阻膜19分別進行繪圖及顯影,藉此兩次形成抗蝕圖案(第1抗蝕圖案15a、第2抗蝕圖案19a),而進行濕式蝕刻。 於此種作為參考例之相位偏移光罩之製造方法中,由於係兩次形成光阻膜(第1抗蝕膜15、第2抗蝕膜19),並對該等光阻膜兩次進行繪圖及顯影,而形成光阻圖案(第1抗蝕圖案15a、第2抗蝕圖案19a),故而於最終所獲得之相位偏移光罩10c中難以使遮光膜圖案14a與相位偏移膜圖案12a之中心吻合。 本發明之相位偏移光罩10a之製造方法係解決於上述作為參考例之相位偏移光罩之製造方法中難以使遮光膜圖案14a與相位偏移膜圖案12a之中心吻合者。即,於本發明之相位偏移光罩10a之製造方法中,使用一次抗蝕膜僅進行一次繪圖及顯影,故而能以遮光膜圖案14a與相位偏移膜圖案12a之中心吻合之方式製造相位偏移光罩10a。 以下,參照圖5詳細地對本發明之相位偏移光罩10a之製造方法進行說明(本發明之相位偏移光罩10b之製造方法亦與此相同)。 <本發明之相位偏移光罩之製造方法> 如圖5所示,首先準備如圖1所示之相位偏移光罩基底10,於相位偏移光罩基底10之遮光膜14上形成第1光阻膜15(圖5(a))。 其次,對第1光阻膜15進行特定圖案之繪圖、顯影處理,而形成抗蝕圖案15a,並將抗蝕圖案15a作為遮罩,藉由蝕刻液A對遮光膜14進行濕式蝕刻,而形成臨時遮光膜圖案14a(圖5(b))。 其次,將臨時遮光膜圖案14a作為遮罩,藉由蝕刻液B對蝕刻阻止膜13進行濕式蝕刻,而形成臨時蝕刻阻止膜圖案13a(圖5(c))。 其次,將臨時蝕刻阻止膜圖案13a作為遮罩,藉由蝕刻液A對相位偏移膜12進行濕式蝕刻,而形成基於相位偏移膜圖案12a之相位偏移部,並藉由對臨時遮光膜圖案14a進行側面蝕刻而形成遮光膜圖案14b(圖5(d))。 最後,去除抗蝕圖案15a,將遮光膜圖案14b作為遮罩,藉由蝕刻液B對臨時蝕刻阻止膜圖案13a進行濕式蝕刻,而形成蝕刻阻止膜圖案13b,於相位偏移膜圖案12a上形成基於蝕刻阻止膜圖案13b與遮光膜圖案14b之遮光部(圖5(e))。 以此方式操作,如圖5(e)所示於透明基板11上具備具有相位偏移部、遮光部、透光部之轉印圖案之相位偏移光罩10a完成。 此處,對蝕刻阻止膜13之膜厚、材料、組成比加以調整、選定,而使蝕刻阻止膜圖案之形成時間為10秒以上且15分鐘以下或10秒以上且10分鐘以下。因此,能抑制製作相位偏移光罩時、尤其是形成蝕刻阻止膜圖案時之蝕刻液B之消耗量,又,因蝕刻液B對透明基板11之接觸時間較短,故而能減少透明基板之損傷,從而可抑制凹缺陷之發生。 再者,說明對蝕刻阻止膜13進行濕式蝕刻時所使用之蝕刻液B。 (蝕刻液B) 對蝕刻阻止膜13進行濕式蝕刻之蝕刻液B只要係可實質上不蝕刻遮光膜14及相位偏移膜12而選擇性地對蝕刻阻止膜13進行蝕刻者,便不加以特別限制。蝕刻液B例如可列舉包含選自氫氟酸、氟矽酸、及氟化氫銨中之至少一者之氟化合物與選自過氧化氫、硝酸、及硫酸中之至少一者之氧化劑的蝕刻液。具體而言可列舉利用純水稀釋氟化氫銨與過氧化氫之混合溶液而獲得之蝕刻液。又,可列舉包含過氧化氫、氟化銨、以及選自磷酸、硫酸及硝酸中至少一者之氧化劑的蝕刻液。具體而言可列舉利用純水稀釋過氧化氫、氟化銨及磷酸之混合溶液而獲得之蝕刻液。 又,根據本發明之相位偏移光罩之製造方法,優點在於以下幾點:僅進行一次繪圖與顯影即可,從而可消除由複數次繪圖步驟所引起之相互對準偏移之影響。尤其優異在可準確地形成微細寬度之相位偏移部16。 又,根據本發明之相位偏移光罩之製造方法,使用一個抗蝕圖案僅進行一次繪圖及顯影,故而能以如圖5(e)之中心線X所示遮光膜圖案14b與相位偏移膜圖案12a之中心吻合之方式製造相位偏移光罩10a。 其次,對本發明之顯示裝置之製造方法進行說明。 <顯示裝置之製造方法> 本發明之顯示裝置之製造方法包括以下步驟: 準備上文所說明之本發明之實施形態之上述相位偏移光罩;及 使用照射曝光之光之顯示裝置製造用曝光裝置,曝光相位偏移光罩之轉印圖案,而將轉印圖案轉印於被轉印體上。 所使用之曝光裝置可為LCD用之標準等倍曝光之曝光裝置。即,藉由使用包含i線、h線、g線之波長區域之光源(亦稱為寬波長光源)作為光源,可獲得充分之照射光量。其中,亦可使用光學濾光片,而僅使用特定波長之光(例如i線)。 曝光裝置之光學系統可將數值孔徑NA設於0.06~0.10,將同調因子σ設於0.5~1.0之範圍。此種曝光裝置一般將3 μm左右設為解像極限。 當然,本發明亦可於使用更大範圍之曝光裝置進行轉印時應用。例如,NA可設於0.06~0.14、或0.06~0.15之範圍。對於NA超過0.08之高解像度之曝光裝置亦產生有需求,本發明亦可應用於該等。 (蝕刻阻止膜(蝕刻終止膜)中之氮之添加與蝕刻速度之關係) 首先,調查包含金屬矽化物之蝕刻阻止膜中之氮之添加與蝕刻速度之關係。 於合成石英玻璃基板(QZ基板)上形成組成比不同之蝕刻阻止膜13(蝕刻終止膜),調查氮之添加與蝕刻速度之關係。將調查結果示於表1。 使用氟化氫銨與過氧化氫之水溶液(22℃)作為蝕刻液,,使用MoSi靶(Mo:Si=1:4),使用氬氣與氮氣作為濺鍍氣體,而於合成石英玻璃基板上形成蝕刻阻止膜(蝕刻終止膜)。 [表1]
10‧‧‧相位偏移光罩基底
10a‧‧‧相位偏移光罩
10b‧‧‧相位偏移光罩
10c‧‧‧相位偏移光罩
11‧‧‧透明基板
12‧‧‧相位偏移膜
12a‧‧‧相位偏移膜圖案
13‧‧‧蝕刻阻止膜
13a‧‧‧蝕刻阻止膜圖案
13b‧‧‧蝕刻阻止膜圖案
14‧‧‧遮光膜
14a‧‧‧遮光膜圖案
14b‧‧‧遮光膜圖案
15‧‧‧第1光阻膜
15a‧‧‧抗蝕圖案
16‧‧‧相位偏移部
17‧‧‧透光部
18‧‧‧遮光部
19‧‧‧第2光阻膜
19a‧‧‧第2抗蝕圖案
140‧‧‧遮光層
141‧‧‧下層部
142‧‧‧上層部
143‧‧‧反射降低層
R‧‧‧邊緣寬度10‧‧‧ phase shift mask base
10a‧‧‧ phase offset mask
10b‧‧‧ phase offset mask
10c‧‧‧ phase offset mask
11‧‧‧Transparent substrate
12‧‧‧ phase offset film
12a‧‧‧ phase offset film pattern
13‧‧‧etching stop film
13a‧‧‧etching stop film pattern
13b‧‧‧etch stop film pattern
14‧‧‧Shade film
14a‧‧‧Shade film pattern
14b‧‧‧Shade film pattern
15‧‧‧1st photoresist film
15a‧‧‧resist pattern
16‧‧‧ phase offset
17‧‧‧Transmission Department
18‧‧‧Lighting Department
19‧‧‧2nd photoresist film
19a‧‧‧2nd resist pattern
140‧‧‧Lighting layer
141‧‧‧ Lower Department
142‧‧‧Upper Department
143‧‧‧Reflection reduction layer
R‧‧‧Edge width
圖1係本發明之相位偏移光罩基底之剖視模式圖。 圖2係本發明之形成有線與間隙圖案之相位偏移光罩之剖視圖(下側)及對應之俯視圖(上側)。 圖3係本發明之形成有孔圖案之相位偏移光罩之剖視圖(下側)及對應之俯視圖(上側)。 圖4(a)~(h)係用以說明參考例之態樣之相位偏移光罩的製造方法之例之圖。 圖5(a)~(e)係用以說明本發明之一實施態樣之相位偏移光罩的製造方法之例之圖。 圖6係本發明之一實施例之相位偏移光罩基底之剖視模式圖。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional schematic view of a phase shift mask substrate of the present invention. 2 is a cross-sectional view (lower side) of the phase shift mask forming the wire and gap pattern of the present invention and a corresponding top view (upper side). 3 is a cross-sectional view (lower side) of a phase shift mask forming a perforated pattern of the present invention and a corresponding top view (upper side). 4(a) to 4(h) are diagrams for explaining an example of a method of manufacturing a phase shift mask of a reference example. 5(a) to 5(e) are views for explaining an example of a method of manufacturing a phase shift mask according to an embodiment of the present invention. Figure 6 is a cross-sectional schematic view of a phase shift mask substrate in accordance with one embodiment of the present invention.
10‧‧‧相位偏移光罩基底 10‧‧‧ phase shift mask base
11‧‧‧透明基板 11‧‧‧Transparent substrate
12‧‧‧相位偏移膜 12‧‧‧ phase offset film
13‧‧‧蝕刻阻止膜 13‧‧‧etching stop film
14‧‧‧遮光膜 14‧‧‧Shade film
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KR20200145954A (en) | 2019-06-21 | 2020-12-31 | 삼성디스플레이 주식회사 | Display apparatus |
JP6987912B2 (en) * | 2020-03-16 | 2022-01-05 | アルバック成膜株式会社 | Mask blanks, phase shift mask, manufacturing method |
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JP6089604B2 (en) * | 2012-11-06 | 2017-03-08 | 大日本印刷株式会社 | Method for manufacturing phase shift mask |
JP6101646B2 (en) * | 2013-02-26 | 2017-03-22 | Hoya株式会社 | Phase shift mask blank and manufacturing method thereof, phase shift mask and manufacturing method thereof, and display device manufacturing method |
JP6324756B2 (en) * | 2013-03-19 | 2018-05-16 | Hoya株式会社 | Phase shift mask blank and method for manufacturing the same, method for manufacturing phase shift mask, and method for manufacturing display device |
JP6198238B2 (en) * | 2013-04-17 | 2017-09-20 | アルバック成膜株式会社 | Method for manufacturing phase shift mask |
JP2015049282A (en) * | 2013-08-30 | 2015-03-16 | Hoya株式会社 | Photomask for manufacturing a display device, manufacturing method of photomask, pattern transfer method, and manufacturing method of display device |
KR101414556B1 (en) * | 2013-12-13 | 2014-07-01 | 주식회사 피케이엘 | Photo mask for improving a resolution and a throughput on flat panel display and method for manufacturing the same |
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2017
- 2017-01-27 JP JP2017013100A patent/JP2017182052A/en active Pending
- 2017-02-24 TW TW106106563A patent/TWI718263B/en active
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JP2017182052A (en) | 2017-10-05 |
KR20170113083A (en) | 2017-10-12 |
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