TW200902461A - Method for removing foreign matter from glass substrate surface and method for processing glass substrate surface - Google Patents
Method for removing foreign matter from glass substrate surface and method for processing glass substrate surface Download PDFInfo
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- TW200902461A TW200902461A TW097113328A TW97113328A TW200902461A TW 200902461 A TW200902461 A TW 200902461A TW 097113328 A TW097113328 A TW 097113328A TW 97113328 A TW97113328 A TW 97113328A TW 200902461 A TW200902461 A TW 200902461A
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- glass substrate
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- ion beam
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- 239000011521 glass Substances 0.000 title claims abstract description 144
- 239000000758 substrate Substances 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 134
- 238000012545 processing Methods 0.000 title claims description 102
- 238000005530 etching Methods 0.000 claims abstract description 67
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims description 149
- 239000012535 impurity Substances 0.000 claims description 96
- 238000011282 treatment Methods 0.000 claims description 69
- 238000000227 grinding Methods 0.000 claims description 30
- 230000003746 surface roughness Effects 0.000 claims description 20
- 238000001020 plasma etching Methods 0.000 claims description 15
- 230000001133 acceleration Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003672 processing method Methods 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012512 characterization method Methods 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- 238000005070 sampling Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 description 14
- 238000005498 polishing Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000001900 extreme ultraviolet lithography Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052902 vermiculite Inorganic materials 0.000 description 7
- 239000010455 vermiculite Substances 0.000 description 7
- 235000019354 vermiculite Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004575 stone Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 101100328843 Dictyostelium discoideum cofB gene Proteins 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004014 SiF4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010922 glass waste Substances 0.000 description 2
- 238000011221 initial treatment Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- -1 ion beam lithography Substances 0.000 description 1
- 238000002164 ion-beam lithography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
- C03C15/02—Surface treatment of glass, not in the form of fibres or filaments, by etching for making a smooth surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- 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
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
- G03F1/24—Reflection masks; Preparation thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/06—Sources
- H01J2237/08—Ion sources
- H01J2237/0812—Ionized cluster beam [ICB] sources
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/30—Electron or ion beam tubes for processing objects
- H01J2237/31—Processing objects on a macro-scale
- H01J2237/3151—Etching
Abstract
Description
200902461 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於自玻璃基板表面移除雜質之方 法，且詳言之係關於一種用於自需要具有高平坦度之玻璃 基板表面（諸如，在半導體製造處理中用於遠紫外線（EUV) 微影之反射型遮罩的玻璃基板）移除雜質的方法。更特定 吕之，本發明係關於一種用於自待藉由伴有在玻璃基板表 面上之射束照射或雷射光照射之方法（諸如，借助於雷射 光照射之離子束敍刻、氣體镇集離子束蝕刻、電聚蝕刻及 奈米磨蝕）處理之玻璃基板表面移除雜質的方法。 又，本發明係關於一種方法，該方法包含：自玻璃基板 表面移除雜t，且接著藉由#有在玻璃基板表面上之射束 照射或雷射光照射之方法（諸如，借助於雷射光照射之離 子束蝕刻、氣體簇集離子束蝕刻、電漿蝕刻及奈米磨蝕） 來處理該玻璃基板表面。 【先前技術】 在微〜技術中，込今已廣泛利用用於藉由將精細電路圖 案轉印於晶圓上而製造積體電路的曝光工具。在趨向於積 體電路之更高整合、更高速度及更高功能化的情況下，積 體電路正在變得更精細。由於此原因，需要曝光工具以高 解析度及長的焦深在晶圓表面上達成電路圖案的影像形 成，且正在推進縮短曝光光源之波長。正在自習知g射線 (波長.436 nm)、！射線（波長：365 及準分子雷射 (波長：248 nm)進—步推進曝光光源，且開始使用ArF準 130467.doc 200902461 分子雷射（波長：193 nm)。又，為了應對下一代積體電路 (其電路線寬度將在100 nm以下），有希望使用f2雷射（波 長.157 nm)作為曝光光源。然而，考慮到，甚至此光源 僅能夠覆蓋至多70 nm之線寬下的產生。 在此技術趨勢下，使用EUV光作為下一代曝光光源之微 影技術視為比45 nm線寬之後的複數代更適用，且正在引 起注意。EUV光指代軟X射線區域或真空紫外線區域之波 #又的光且具體s之意謂具有約0.2至1〇〇 nm之波長的 光。目前，正研究使用13.5 nm作為微影光源。此Euy微 影（本文中簡寫為”EUVL”）之曝光原理在使用投影光學系統 轉印遮罩圖案方面等同於習知微影。然而’在EUV光之能 區中，由於不存在能夠經由其透射光的材料，所以不可使 用折射光學系統，但必然使用反射光學系統（參見專利文 獻1)。 待用於EUVL之遮罩基本上經組態以具有：⑴玻璃基 板，（2)形成於玻璃基板上之反射性多層薄膜，及（3)形成 於反射性多層薄膜上的吸收體層。作為反射性多層薄膜， 使用具有一結構(其中對於曝光光之波長具有不同折射率 的複數種材料以奈米尺度循環層疊）之多層薄膜，且已知 Mo及S4代表性材料。又，已研％TaA<^作為吸收體層之 材料。作為玻璃基板’為了即使在由EUV光照射時仍不會 產生應變，需要具有低熱膨脹係數之材料，且已研究使用 具有低熱膨脹係數之玻璃或具有低熱膨脹係數之結晶玻 璃。在此說明書中，具有低熱膨脹係數之玻璃及具有低熱 130467.doc 200902461 膨脹係數之結晶玻璃統稱為，,低膨脹玻璃，,或"超低膨脹玻 璃-’。 作為待用作EUVL之遮罩之低膨脹玻璃或超低膨脹玻 璃，最廣泛地使用石英玻璃，石英玻璃主要由Si02構成且 為了減小玻璃之熱膨脹係數而作為摻雜劑向其添加Ti〇2、 Sn〇2 或 Zr02。 玻璃基板藉由以尚精度處理此玻璃或結晶玻璃之原料並 對其進行洗滌而製造。在處理玻璃基板之狀況下，一般而 言，玻璃基板表面以相對較高之處理速率進行預研磨直至 其具有預定平坦度及表面粗糙度；藉由洗滌移除諸如由預 研磨產生之研磨廢棄物的雜質；且接著藉由具有較高處理 精度之方法精處理玻璃基板表面以便具有所要平坦度及表 面粗糙度。作為待用於精處理之具有高處理精度之方法， 較佳使用伴有在玻璃基板表面上之射束照射或雷射光照射 之方法（諸如，借助於雷射光照射之離子束蝕刻、氣體簇 集離子束蝕刻、電漿蝕刻及奈米磨蝕）。 然而’存在藉由洗條尚未完全移除之雜質殘存之狀況； 及雜質在洗滌之後新附著於玻璃基板表面上的狀況。當存 在此雜質之玻璃基板表面藉由伴有在玻璃基板表面上之射 束照射或雷射光照射之方法（諸如，借助於雷射光照射之 離子束蝕刻、氣體簇集離子束蝕刻、電漿蝕刻及奈米磨 钕）進行精處理時’存在玻璃基板表面上存在雜質之部八 未被處理之問題，且自玻璃基板表面移除雜質的後續洗膝 導致玻璃之凸狀缺陷的產生。 130467.doc 200902461 專利文獻 1 : JP-T-2003-505891 【發明内容】 為了解決先前技術之前述問題，本發明之一目標為提供 一種用於自玻璃基板表面移除雜質之方法，該玻璃基板表 面待藉由伴有在該玻璃基板表面上之射束照射或雷射光照 =之方法（諸如，借助於雷射光照射之離子束蝕刻、氣體 簇集離子束蝕刻、電漿蝕刻及奈米磨蝕）進行精處理。200902461 IX. Description of the Invention: [Technical Field] The present invention relates to a method for removing impurities from a surface of a glass substrate, and more particularly to a surface of a glass substrate for which high flatness is required ( A method of removing impurities, such as a glass substrate for a reflective mask of extreme ultraviolet (EUV) lithography in a semiconductor manufacturing process. More specifically, the present invention relates to a method for self-injection by beam irradiation or laser irradiation on a surface of a glass substrate (such as ion beam lithography, gas gathering by means of laser irradiation) A method of removing impurities on the surface of a glass substrate treated by ion beam etching, electropolymer etching, and nano abrasion. Still further, the present invention relates to a method comprising: removing impurities t from the surface of a glass substrate, and then by means of beam irradiation or laser light irradiation on the surface of the glass substrate (such as by means of laser light) The surface of the glass substrate is treated by ion beam etching, gas cluster ion beam etching, plasma etching, and nano abrasion. [Prior Art] In the micro-technology, an exposure tool for manufacturing an integrated circuit by transferring a fine circuit pattern onto a wafer has been widely used. Integrated circuits are becoming more sophisticated as they tend to be more integrated, higher speed, and more functional. For this reason, an exposure tool is required to achieve an image formation of a circuit pattern on a wafer surface with high resolution and a long depth of focus, and is propelling to shorten the wavelength of the exposure light source. I am learning the g-ray (wavelength .436 nm),! The ray (wavelength: 365 and excimer laser (wavelength: 248 nm) advances the exposure source and starts to use the ArF quasi 130467.doc 200902461 molecular laser (wavelength: 193 nm). In addition, in order to deal with the next generation of integrated The circuit (with a circuit line width below 100 nm) is promising to use an f2 laser (wavelength .157 nm) as the exposure source. However, it is considered that even this source can only cover a line width of up to 70 nm. Under this technology trend, the lithography technique using EUV light as the next-generation exposure source is considered to be more suitable than the complex generation after the 45 nm line width, and attention is being paid. EUV light refers to the soft X-ray region or the vacuum ultraviolet region. The light and the specific s mean light having a wavelength of about 0.2 to 1 〇〇 nm. Currently, 13.5 nm is being used as a lithographic light source. This Euy lithography (abbreviated as "EUVL" in this paper) The principle of exposure is equivalent to conventional lithography in transferring a mask pattern using a projection optical system. However, in the energy region of the EUV light, since there is no material through which light can be transmitted, a refractive optical system cannot be used. It is inevitable to use a reflective optical system (see Patent Document 1). The mask to be used for EUVL is basically configured to have: (1) a glass substrate, (2) a reflective multilayer film formed on a glass substrate, and (3) formation. An absorber layer on a reflective multilayer film. As the reflective multilayer film, a multilayer film having a structure in which a plurality of materials having different refractive indices for wavelengths of exposure light are cyclically laminated on a nanometer scale is used, and Mo is known. And S4 representative material. Further, %TaA<^ has been studied as a material of the absorber layer. As a glass substrate, in order to prevent strain even when irradiated by EUV light, a material having a low coefficient of thermal expansion is required, and has been studied. A glass having a low coefficient of thermal expansion or a crystallized glass having a low coefficient of thermal expansion. In this specification, a glass having a low coefficient of thermal expansion and a crystallized glass having a low heat 130467.doc 200902461 expansion coefficient are collectively referred to as a low-expansion glass, or " Ultra-low expansion glass - '. As the low expansion glass or ultra low expansion glass to be used as a mask for EUVL, the most extensive Quartz glass, quartz glass is mainly composed of SiO 2 and Ti 2 , Sn 〇 2 or Zr 02 is added as a dopant to reduce the thermal expansion coefficient of the glass. The glass substrate is processed by the glass or crystal glass with a precision And manufacturing it by washing. In the case of processing the glass substrate, generally, the surface of the glass substrate is pre-ground at a relatively high processing rate until it has a predetermined flatness and surface roughness; The impurities of the grinding waste generated by the pre-grinding; and then the surface of the glass substrate is refined by a method having high processing precision to have desired flatness and surface roughness. As a method having high processing precision to be used for finishing, it is preferred to use a method of beam irradiation or laser irradiation on the surface of a glass substrate (such as ion beam etching by means of laser irradiation, gas clustering) Ion beam etching, plasma etching and nano abrasion). However, there is a condition in which impurities remaining by the washing strip have not been completely removed; and a state in which the impurities are newly attached to the surface of the glass substrate after washing. When the surface of the glass substrate in which the impurity is present is irradiated by laser beam or laser light on the surface of the glass substrate (such as ion beam etching by laser irradiation, gas cluster ion beam etching, plasma etching) And nano-milling) When the finishing treatment is performed, there is a problem that the portion of the surface of the glass substrate where impurities are not treated, and the subsequent washing of the impurities from the surface of the glass substrate causes the occurrence of convex defects of the glass. 130467.doc 200902461 Patent Document 1: JP-T-2003-505891 SUMMARY OF THE INVENTION In order to solve the aforementioned problems of the prior art, it is an object of the present invention to provide a method for removing impurities from a surface of a glass substrate, the glass substrate The surface is to be subjected to a method of beam irradiation or laser illumination on the surface of the glass substrate (such as ion beam etching by means of laser irradiation, gas cluster ion beam etching, plasma etching, and nano abrasion). ) Perform fine processing.
本發明之另-目標為提供—種方法，其中在自玻璃基板 表面移除雜質之後，藉由伴有在玻璃基板表面上之射束照 射或雷射光照射之方法（諸如，借助於雷射光照射之離子 束触刻、氣體簇集離子束㈣、電漿㈣及奈$磨⑷處 理該玻璃基板表面。 為了達成前述目標，本發明提供—種用於自玻璃基板表 面移除雜質之方法，該方法包含使玻璃基板表面在5至15 keV之加速電壓下經受氣體蔟集離子束蝕刻。Another object of the present invention is to provide a method in which, after removing impurities from the surface of a glass substrate, by irradiation with a beam or laser light on the surface of the glass substrate (such as by means of laser irradiation) The ion beam etch, the gas cluster ion beam (4), the plasma (4), and the neat (4) process the surface of the glass substrate. To achieve the foregoing object, the present invention provides a method for removing impurities from a surface of a glass substrate, The method comprises subjecting the surface of the glass substrate to gas concentrating ion beam etching at an accelerating voltage of 5 to 15 keV.
又’本發明提供—種用於自玻璃基板表面移除雜質之方 :，該方法包含以選自由〇2、Ar、B、c〇2、N2、N2〇M 彳且成之群中至少—氣體作為氣體源，使該玻璃基板 表面經受氣體簇㈣子束钱刻。 在本發明中，本1 丁 ^ 先則兩個段落中描述之方法中之每一者在 下文中稱為"本發明之雜f移除方法”。 在本發明之雜暂全 ’、移除方法中，較佳在蝕刻量為20 nm以 下之條件下執行氣體義集離子束㈣。 在本發明之雜 ’、移除方法中，較佳玻璃基板由在2(TC或 130467.doc 200902461 5〇°C 至 80。〇具有 〇 士 30 成0 PPb/ C之熱膨脹係數的低膨脹玻璃製 在本發明之雜質移除方法中，較佳在執行氣體蔟集離子 束钮刻前的玻璃基板表面具有5 nm以下之表面粗糙度 (Rms)。 在本發明之雜質移除方 以上之條件下執行氣體簇集離子束蝕刻。 在本發明之雜質移除方法中，較佳使由玻璃基板之法線 與待入射至玻璃基板表面之氣體蔟集離子束所形成的角度 保持3至60度，同時執行氣體簇集離子束蝕刻。 此處，較佳在使麵基録㈣持於相對於水平方向成 3至60度面朝下之狀態，同時執行氣體簇集離子束飯刻。 又，本發明提供—種處理玻璃基板表面之方法，該方法 包含以下步驟： 藉由本發明之雜質移除方法移除麵基板表面上的雜 質；及 藉由選自由離子束蝕刻、氣體簇集離子束蝕刻、電衆蝕 刻及奈米純所組成之群巾的處理方法來處理玻璃基板表 面（此方法在下文中將稱為”本發明之處理方法〇广）。 在本發明之處理方法r η φ， ()中處理方法較佳為氣體簇集 離子束蝕刻。 此處，較佳在超出15keV之加速電壓下，使用選自由下 列混合氣體所組成之群中之混合氣體作為來源氣體執行處 理步驟中之氣體簇集離子束㈣：％與之混合氣體， 130467.doc 200902461 SF6、Ar與02的混合氣體，NF3與〇2之混合氣體，NF3、心 與〇2之混合氣體，NF3與N2之混合氣體及NF3、^與乂的 混合氣體。 來源氣體較佳為選自由下列混合氣體所組成之群中的任 一者：SF0與A之混合氣體，St、心與〇2之混合氣體， NF3與〇2的混合氣體及NI?3、^與之混合氣體。 又，本發明提供一種用於處理玻璃基板表面之方法，該 方法包含以下步驟： 里測玻璃基板表面之平坦度； 藉由本發明之雜質移除方法移除玻璃基板表面上的雜 質；及 藉由選自由離子束蝕刻、氣體簇集離子束蝕刻、電漿蝕 刻及奈米磨蝕所組成之群中的處理方法來處理玻璃基板表 面， 其中，在處理該玻璃基板表面之步驟中，基於自量測平 -度之步驟獲得之結果來為玻璃基板之每一處設定玻璃基 板表面的處理條件（此方法在下文中將稱為"本發明之處理 方法（2)，’）。 在本發明之處理方法（2)中’該處理方法較佳為離子束 蝕刻、I體簇集離子束钱㈣電漿姓刻；基於自量測玻璃 基板表面之平坦度之步驟獲得之結果指定存在於玻璃基板 面上之波紋之覓度；且藉由一射束來處理玻璃基板表 面’ 4射束具有以半高寬（FWHM)計不大於該波紋之寬度 的射束直徑。 130467.doc 200902461 此處，射束直徑之FWHM值較佳不大於波紋寬度的1/2。 在本發明之處理方法（2)中，較佳處理方法為氣體簇集 離子束敍刻’且在超出丨5 keV之加速電壓下，使用選自由 下列混合氣體所組成之群中之混合氣體作為來源氣體執行 處理步驟中之氣體簇集離子束蝕刻：SF6與〇2之任一混合 氣體，SF6、Ar與〇2的混合氣體，nf3與02之混合氣體， 、 NI?3、八续〇2之混合氣體，NF3與N2之混合氣體及NF3、Ar 與N2的混合氣體。 來源氣體更佳係選自由下列混合氣體所組成之群中的任 一者.SF6與〇2之混合氣體，SF6、Ar與〇2之混合氣體， NF3與〇2的混合氣體及NF3、αγ與〇2之混合氣體。 在本發明之處理方法（1)及（2)中，較佳在處理玻璃基板 表面之步驟之後，執行第二處理步驟以改善玻璃基板表面 的表面粗縫度。 較佳地，作為第二處理步驟，在3 keV以上且小於3〇 ( keV之加速電壓下單獨使用〇2氣體或使用A與至少一選自 由Ar、C0及C〇2所組成之群之氣體的混合&體為來源氣體 執行氣體簇集離子束蝕刻。 於1至60 gf/cm2之表面壓 之射束照射 較佳地，作為第二處理步驟， 力執行使用研磨漿的機械研磨。Further, the present invention provides a method for removing impurities from a surface of a glass substrate: the method comprises at least one selected from the group consisting of 〇2, Ar, B, c〇2, N2, N2〇M 彳The gas acts as a gas source, and the surface of the glass substrate is subjected to a gas cluster (four) beam. In the present invention, each of the methods described in the two paragraphs is hereinafter referred to as "the heterogeneous f removal method of the present invention". In the method, the gas-sense ion beam (4) is preferably performed under the condition that the etching amount is 20 nm or less. In the method of removing and removing the present invention, the preferred glass substrate is 2 (TC or 130467.doc 200902461 5 〇°C to 80. 低 a low-expansion glass having a thermal expansion coefficient of 30 to 0 PPb/C of the gentleman. In the impurity removing method of the present invention, preferably, the surface of the glass substrate before the gas concentrating ion beam button is performed It has a surface roughness (Rms) of 5 nm or less. Gas cluster ion beam etching is performed under the conditions of the impurity removing side of the present invention. In the impurity removing method of the present invention, the method of using a glass substrate is preferred. The line forms an angle of 3 to 60 degrees with the gas collected by the gas beam to be incident on the surface of the glass substrate while performing gas cluster ion beam etching. Here, it is preferred to hold the surface base (4) in a horizontal direction. 3 to 60 degrees face down, while Further, the present invention provides a method for treating a surface of a glass substrate, the method comprising the steps of: removing impurities on a surface of the surface substrate by the impurity removing method of the present invention; A method of treating a glass substrate by a free ion beam etching, a gas cluster ion beam etching, a plasma etching, and a group processing method consisting of nano pure (this method will hereinafter be referred to as "the processing method of the present invention"). In the treatment method r η φ, () of the present invention, the treatment method is preferably gas cluster ion beam etching. Here, preferably, at an acceleration voltage exceeding 15 keV, a group selected from the group consisting of the following mixed gases is used. The mixed gas is used as the source gas to perform the gas clustering ion beam in the processing step (4): % mixed gas, 130467.doc 200902461 SF6, mixed gas of Ar and 02, mixed gas of NF3 and 〇2, NF3, heart and 〇2 a mixed gas, a mixed gas of NF3 and N2, and a mixed gas of NF3, 乂 and 乂. The source gas is preferably selected from any group consisting of the following mixed gases: SF0 and a mixed gas of A, a mixed gas of St, a core and a ruthenium 2, a mixed gas of NF3 and 〇2, and a mixed gas of NI?3, and the like. Further, the present invention provides a method for treating the surface of a glass substrate, the method The method comprises the steps of: measuring the flatness of the surface of the glass substrate; removing impurities on the surface of the glass substrate by the impurity removing method of the present invention; and by selecting from ion beam etching, gas cluster ion beam etching, plasma etching, and a treatment method in a group consisting of nano-abrasives to treat the surface of the glass substrate, wherein in the step of processing the surface of the glass substrate, each of the glass substrates is set based on the result obtained by the self-measurement-degree step Processing conditions of the surface of the glass substrate (this method will hereinafter be referred to as "treatment method (2), ') of the present invention. In the treatment method (2) of the present invention, the treatment method is preferably ion beam etching, I-organ cluster ion beam (four) plasma surname; the result obtained by the step of self-measurement of the flatness of the surface of the glass substrate is specified. The thickness of the corrugations present on the surface of the glass substrate; and the surface of the glass substrate treated by a beam '4 beam has a beam diameter not greater than the width of the corrugation in terms of full width at half maximum (FWHM). 130467.doc 200902461 Here, the FWHM value of the beam diameter is preferably not more than 1/2 of the width of the corrugation. In the treatment method (2) of the present invention, the preferred treatment method is gas clustering ion beam characterization" and at an acceleration voltage exceeding 丨5 keV, using a mixed gas selected from the group consisting of the following mixed gases as The source gas performs the gas cluster ion beam etching in the processing step: any mixed gas of SF6 and 〇2, SF6, a mixed gas of Ar and 〇2, a mixed gas of nf3 and 02, NI?3, and Continuation 2 The mixed gas, a mixed gas of NF3 and N2, and a mixed gas of NF3, Ar and N2. Preferably, the source gas is selected from the group consisting of the following mixed gases: a mixed gas of SF6 and 〇2, a mixed gas of SF6, Ar and 〇2, a mixed gas of NF3 and 〇2, and NF3, αγ and Mixture of 〇2. In the treatment methods (1) and (2) of the present invention, preferably after the step of treating the surface of the glass substrate, the second treatment step is performed to improve the surface roughness of the surface of the glass substrate. Preferably, as the second processing step, the gas of 〇2 gas alone or the use of A and at least one group selected from the group consisting of Ar, C0 and C〇2 is used at an acceleration voltage of 3 keV or more and less than 3 〇 (keV). The mixing & body performs gas cluster ion beam etching for the source gas. Beam irradiation at a surface pressure of 1 to 60 gf/cm 2 is preferably performed as a second processing step, and mechanical grinding using the slurry is performed.
在藉由伴有在玻璃基板表面上 又’本發明提供一 基板’其中基板表面具有50 nm 超出1.5 nm的凸狀玻璃缺陷。 根據本發明， 130467.doc 12 200902461 或雷射光照射之方法（諸如，供 左（漘如k助於雷射光照射之離 雀虫刻、氣體減集離子束敍刻、電i ^ β & 1 , 電漿蝕刻及奈米磨蝕）精處 玻璃基板表面之狀況下，有可能防止在處理之後在破璃 基板表面上產生凸狀玻璃缺陷，且將玻璃基板表面處理為 具有極佳平坦度及表面粗糙度的表面。 【實施方式】 本發明之雜質移除方法，係關於—㈣於自待以伴有在 玻璃基板表面上照射射束或照射雷射光之方法（諸如，借 助於雷射光照射之離子束㈣、氣體簇集離子束银刻、^ 漿钮刻及奈米磨钮）來進行精處理之玻璃基板表面（此玻璃 基板表面亦將稱為，’處理表面，，)_即精處理之前的處理表面-移除雜質的方法。 在執行精處理之前會洗滌此類處理表面。在此情形中， 有時會有洗料未完全去除之雜該留，有時會有在洗務 後新附著於玻璃基板表面上的雜質。本發明之雜質移除方 法旨在移除此類雜質。 本發明之雜質移除方法之目標雜質，係指藉由凡得瓦力 (van der Waals f〇uce)附著於處理表面上的物質而非藉由 化學鍵固定於處理表面上的物質’且其大小通常為1至2 μπι左右或更小。 本發明之雜質移除方法之目標玻璃基板，為EUVL用反 射型遮罩的玻璃基板，EUVL能夠對應積體電路更高的積 集度及更尚的解析度。欲使用於此應用之玻璃基板為具有 小熱膨脹係數及小散射的玻璃基板。玻璃基板較佳由在 130467.doc •13· 200902461 20 C或在50 C至80。。具有〇士30 ppb/。。之熱膨脹係數的低膨 服玻璃製成，且更佳由在2(rc或在5〇t：至贼具有㈣〇 ppb/ C之熱膨脹係數的超低膨脹玻璃製成。 玻璃基板關於形狀、大小及厚度等並不特定地受到限 制。在EUVL用反射型遮罩的基板之狀況下，考慮到矩形 平坦形狀，玻璃基板之形狀為矩形板狀體。 較佳地，在為本發明之雜質移除方法之目標的玻璃基板 ί \ 中，處理表面經初步處理以便具有預定平坦度及表面粗糖 度。 雖然待用於處理表面之初步處理的離子束㈣、氣體霧 集離子束钱刻、電㈣刻及奈米磨姓能夠將玻璃基板表面 處理為具有極佳平坦度及表面粗链度的表面，但考慮 理速率，尤其在處理具有大面積之玻璃基板表面之狀況下 的處理速率’此等處理方法劣於習知機械研磨。另—方 面，下文詳細描述之本發明之雜質移除方法為一種用於移 除存在於處理表面上的雜質而實質上不對處理表面進行處 理的方法。由於此原因，較佳在執行本發明之雜質移除方 法之前’藉由具有相對較高之處理速率的處理方法對處理 表面進行初步處理以使其具有預定平坦度及表面粗Μ。 待用於初步處理之處理方法不受特定限制，而可在待用 於處理玻璃表面之已知處理方法中廣泛地選擇。然而，藉 由使用具有大處理速率及大表面面積之研磨襯塾，有可 次具有大面積的研磨處理，且因此通常使用機_ 1法。如本文中提及之機械研磨方法除僅借助於使用磨 130467.doc 200902461 r 粒（abrasive grain)之研磨功能外，亦包括使用研磨漿的方 法，該方法組合地利用使用磨粒之研磨功能及使用化學物 質的化學研磨功能。機械研磨方法可為拋光與研磨中之任 一者，且可自已知研磨工具及研磨劑中適當選擇待使用之 研磨工具及研磨劑。當使用機械研磨方法時，為了使得處 理速率為大的’在拋光狀況下，較佳在至gf/cm2之表 面壓力下執行拋光，且更佳在40至60 gf/cm2之表面壓力下 執行拋光；而在研磨狀況下，較佳在6〇至14〇 gf/cm2之表 面壓力下執行研磨，且更佳在80至12〇 gf/cm2之表面壓力 下執行研磨。拋光較佳經執行以提供1〇〇至3〇〇 μίη之拋光 里且研磨較佳經執彳于以提供1至60 μηι的研磨量。 在執行初步處理之狀況下，初步處理之後的處理表面較 佳具有5 nm以下之表面粗糙度（Rms)，且更佳具有i議以 下的表面粗糙度。如本說明書中提及之表面粗趟度意謂相 對於1至10平方微米之面積藉由原子力顯微鏡f〇rce ―㈣〒）量測的表面粗链度。當初步處理之後的玻璃基 板之表面《度超出5 nm時，在執行本發明之雜質移除方 =後花費相當長之時間週期來精處理處理表面以具有預 疋平坦度及表面粗糖唐，日田山 且因此，此變為成本增加的因 I。 面^明之㈣移除方法特徵在於，藉由在相對於處理表 岁|J停件^刻里之#曰定條件（此條件在下文中將稱為”低姓 :;:處:表執行氣體簇集離子束(下文 面移除雜質’同時使得處理表面之處理量極 J30467.doc 200902461 低。The present invention provides a substrate having a convex glass defect of 50 nm exceeding 1.5 nm by being accompanied by a substrate on the surface of the glass substrate. According to the invention, 130467.doc 12 200902461 or a method of laser illumination (such as for the left (such as k assisted by laser light, the gas subtraction ion beam characterization, electric i ^ β & 1 , plasma etching and nano-abrasive) in the condition of the surface of the glass substrate, it is possible to prevent the occurrence of convex glass defects on the surface of the glass substrate after the treatment, and the surface of the glass substrate is treated to have excellent flatness and surface Roughness of the surface. [Embodiment] The method for removing impurities of the present invention relates to - (d) a method of illuminating a beam or irradiating a laser beam on a surface of a glass substrate (such as by means of laser light irradiation) Ion beam (four), gas cluster ion beam silver engraving, ^ pulp button engraving and nano grinding button) for finishing the surface of the glass substrate (this glass substrate surface will also be called, 'processing surface,)) Previous treatment surface - method of removing impurities. This type of treated surface will be washed before performing the finishing treatment. In this case, sometimes the washing material is not completely removed, sometimes there will be after washing new Impurities attached to the surface of the glass substrate. The impurity removal method of the present invention is intended to remove such impurities. The target impurity of the impurity removal method of the present invention refers to van der Waals f〇uce a substance attached to the treated surface rather than a substance fixed to the treated surface by a chemical bond' and having a size of usually about 1 to 2 μπι or less. The target glass substrate of the impurity removing method of the present invention is for EUVL The glass substrate of the reflective mask, EUVL can correspond to the higher integration degree and more resolution of the integrated circuit. The glass substrate to be used for this application is a glass substrate with a small thermal expansion coefficient and small scattering. Good by 130467.doc •13· 200902461 20 C or 50 C to 80.. With a gentle expansion of 30 ppb/. of low expansion glass, and better by 2 (rc or in 5) 〇t: It is made of ultra-low expansion glass with a thermal expansion coefficient of (4) 〇ppb/ C. The glass substrate is not particularly limited in shape, size and thickness, etc. In the case of a substrate with a reflective mask of EUVL Considering the rectangle In a flat shape, the shape of the glass substrate is a rectangular plate-like body. Preferably, in the glass substrate λ which is the object of the impurity removing method of the present invention, the treated surface is subjected to preliminary treatment so as to have a predetermined flatness and surface roughness. Although the ion beam (4) to be used for the initial treatment of the surface, the gas mist collecting ion beam, the electric (four) engraving, and the nanomilling name can treat the surface of the glass substrate as a surface having excellent flatness and surface thick chain, However, considering the processing rate, especially in the case of processing the surface of a glass substrate having a large area, such processing methods are inferior to conventional mechanical grinding. In addition, the impurity removing method of the present invention described in detail below is a kind. A method for removing impurities present on a treated surface without substantially treating the treated surface. For this reason, it is preferred to subject the treated surface to a predetermined flatness and surface roughness by a treatment method having a relatively high processing rate before performing the impurity removing method of the present invention. The treatment method to be used for the preliminary treatment is not particularly limited, and can be widely selected among known treatment methods to be used for treating the glass surface. However, by using a ground lining having a large processing rate and a large surface area, there is a large-area grinding treatment, and thus the machine_1 method is usually used. The mechanical grinding method as referred to herein also includes a method of using a slurry, in addition to the grinding function using only abrasive grinding, and the use of the abrasive grinding function and Chemical polishing function using chemicals. The mechanical polishing method may be any one of polishing and grinding, and the abrasive tool and the abrasive to be used may be appropriately selected from known abrasive tools and abrasives. When the mechanical grinding method is used, in order to make the treatment rate large, in the polishing condition, polishing is preferably performed under a surface pressure of gf/cm2, and polishing is preferably performed at a surface pressure of 40 to 60 gf/cm2. In the case of grinding, it is preferred to perform grinding at a surface pressure of 6 to 14 〇 gf/cm 2 , and more preferably at a surface pressure of 80 to 12 〇 gf/cm 2 . Polishing is preferably performed to provide a polishing of from 1 Torr to 3 Å μίη and that the polishing is preferably performed to provide an abrasive amount of from 1 to 60 μm. In the case where the preliminary treatment is performed, the treated surface after the preliminary treatment preferably has a surface roughness (Rms) of 5 nm or less, and more preferably has a surface roughness below. The surface roughness as referred to in the specification means the surface thick chain measured by an atomic force microscope f〇rce - (tetra) 相 with respect to an area of 1 to 10 square micrometers. When the surface of the glass substrate after the preliminary treatment exceeds 5 nm, it takes a considerable period of time after performing the impurity removal side of the present invention to finish the treated surface to have pre-flatness and surface roughness. Tianshan and therefore, this becomes the cause of cost increase. The feature of the (4) removal method is characterized in that the condition is determined by the # in the case of the processing table (this condition will be hereinafter referred to as "low surname:;:: table: gas cluster execution" Collecting the ion beam (removing the impurity below) also makes the processing surface of the treated surface extremely low J30467.doc 200902461.
如本文中提及之GCIB蝕刻為一種方法，其中在常溫及 大氣壓力下處於氣態之反應性物質（來源氣體）經由膨脹型 喷嘴以受壓狀態噴射至真空裝置中以形成氣體镇集（該氣 體簇集接著在由電子照射之後即被離子化），且將所得 GCIB照射於目標上以達成㈣。該氣體簇集通常由大的 原子群或分子群構成，大的原子群或分子群由數千原子或 分子構成。在本發明之雜質移除方法中，藉由在處理表面 上執行GCIB蝕刻，當氣體簇集與處理表面碰撞時，歸因 於與固體之相互作用而產生多次碰撞效應，籍此自處理表 面移除雜質。接著，由於在低㈣條件下在處理表面上執 行GCIB蝕刻，所以處理表面實質上未被處理。 在本發明之雜質移除方法中，藉由指定處理表面上雜質 存在之處，可在此處選擇性地執行gcib蝕刻。然而，難 、疋八有、1至2 或更小大小之精細雜質處且難以在 此處選擇性地執行GCIB_。因此，一般而纟，在低敍 刻條件下在整個處理表面上執行gcib蝕刻。在該狀況 有必要在處理表面上掃描GCIB。作為掃描Gcib之方 法，已知光柵掃描（luster sc_ing)及螺旋掃描， 此等方法中之任一者。 更用 發月之雜質移除方法之第-實施例中，為了在低蝕 二條件下在處理表面上執行GC_，將用於施加至加 二極之加速電壓控制在5至15 keV。在該狀況下’為了 精處理破璃基板表面，在執行沉職刻中使用之來源氣 130467.doc •16· 200902461 體可為習知地使用之來源氣體。 此匕ι知來源氣體之特定實The GCIB etching as referred to herein is a method in which a reactive substance (source gas) which is in a gaseous state at normal temperature and atmospheric pressure is sprayed into a vacuum device via an expansion nozzle to form a gas town (the gas) The clusters are then ionized after being irradiated by electrons, and the resulting GCIB is irradiated onto the target to achieve (4). The gas cluster is usually composed of a large atomic group or a group of molecules, and a large atomic group or group of molecules is composed of thousands of atoms or molecules. In the impurity removing method of the present invention, by performing GCIB etching on the processing surface, when the gas cluster collides with the processing surface, multiple collision effects are generated due to interaction with the solid, thereby self-treating the surface Remove impurities. Next, since the GCIB etch is performed on the treated surface under low (four) conditions, the treated surface is substantially untreated. In the impurity removing method of the present invention, the gcib etching can be selectively performed here by specifying the presence of impurities on the surface. However, it is difficult, complicated, fine impurities of 1 to 2 or less, and it is difficult to selectively perform GCIB_ here. Therefore, in general, gcib etching is performed on the entire processing surface under low-synchronization conditions. In this situation it is necessary to scan the GCIB on the treated surface. As a method of scanning Gcib, raster scanning (luster sc_ing) and helical scanning are known, and any of these methods. In the first embodiment in which the impurity removal method of the moon is used, in order to perform GC_ on the treated surface under the low etching condition, the acceleration voltage for application to the added diode is controlled to 5 to 15 keV. In this case, the source gas used in the execution of the sinking surface for the purpose of finely processing the surface of the glass substrate 130467.doc •16·200902461 is a source gas which is conventionally used. This 匕ι knows the source of the gas
例包括 SF6、nf3、CHF3、CF4、Γ C 4 、C3F8、C4F6、SiF4及 COF2。可單獨或混合地使用此等氣體。 藉由將待施加至加速電極之加速電壓控制“Μ keV，甚至在為了精處理處理表 m ^ 疫衣面而在執行GCIB蝕刻中使 用；白知地使用之來源氣體的狀況 σ ^ 卜處理表面上之蝕刻量 亦足夠低，且存在於處理表面 之雜慮可被移除而實質上 ί 不處理處理表面。在加速電壓 沪兹隹叙“ * 疋电’幻、於5 keV之狀況下，當氣 體族集與處理表面碰撞時，動 表面上之雜質視雜質之大^ 小的，使得存在於處理 有约… 小而不可被移除。具體言之，具 有为1 μιη至2 μηι之大小之雜晳 屮m', 雜質不可被移除。在加速電壓超 出1 5 keV之狀況下，當氣 .,.m 乱體族集與處理表面碰撞時，動能 為大的。因此，處理表面上 ^勒月b 表面上之精細雜質之作田@ +/乍用比移除存在於處理 於上面之严理* 顯者；且類似地，在雜質存在 僅雜質存在之處理类品 处里之狀況下， 卢神主 表面之部分保持未被蝕刻，從而 心、面(已藉由洗滌或類似 μ ^ π 飞目邊處理表面移除雜暂、 上產生凸狀缺陷的問題。 秒除雜質） 加速電屢更佳為5keV至Ι〇Μ。 在本發明之雜質移除方法之 刻條件下在處理矣 β，尹，為了在低蝕 bB、C〇2 Ν〇表及面上執行咖敍刻，使用選自〇2、 一氣體作為氣體2源^化·如’叫及^。）中之至少 表面碰撞時，复：GCW蝕刻。當此氣體物質與處理 1致化學反應’且敍刻處理表面之作 I30467.doc 200902461 和弱在使用此氣體物質作為來源氣體執行GCIB蝕刻 片’兄下存在於處理表面上之雜質可被移除，而實質上 不處理處理表面。 在本發明之雜質移除方法之第二實施例中，並不特定限 制用於向加速電極施加具有極弱蝕刻作用之氣體物質的加 速電屢。然;而’自移除存在於處理表面上之雜質而不實質 上處理處理表面之觀點’加速電壓為15 W以上為較佳 的。加速電壓更佳為20 keV以上，且進一步較佳為3〇 W 以上在加速電壓小於15 keV狀況下，當氣體簇集與處理 表面碰撞時’動能為小的，且因&，視雜質之大小而定， 存在於處理表面上存在之雜f不可被移除的可能性。然 而，即使當加速電壓小於15 keV時，藉由調整竊集大小、 劑量、照射時間等’可移除存在於處理表面上之雜質。 根據本發明之雜質移除方法的前述第一實施例及第二實 施例，由於在低触刻條件下在處理表面上執行gCIB* 所以可移除存在於處理表面上之雜質而實質上不處理 處理表面。如本文中提及之低蝕刻條件較佳為蝕刻量在20 nm以下之條件，且更佳為钱刻量在⑺麵以下之條件。 在本發明之雜質移⑨方法之第一實施例及第三實施例 中，可根據來源氣體之種類、肖施加至加速電極之加速電 壓等而適當選擇照射條件(例如，簇集大小、待施加至 GCIB蝕刻裝置之離子化電極以離子化簇集之離子化電流 及gCIB的劑量）。較佳地，在蔟集大小為2,〇〇〇以上之條件 下執行GCIB蝕刻。當簇集大小為2,麵以上時，由於相對 130467.doc 200902461 較大之氣體簇集與處理表 „ 面亚撞，所以可預期歸因於多次 碰撞效應而增強移除存 夕人 處表面上之雜質的效應。簇 集大小更佳為3，_以上，且尤佳為5,刚以上。 在：發明之雜質移除方法之第一實施例及第二實施例 較佳使GCIB自傾斜方向照射於處 GCIB自傾斜方向照射 田使 …址 、慝理表面上時，可預期歸因於多 -人碰撞效應而增強銘降六 ^ _ 移除存在於處理表面上之雜質的效應。 圖1為說明使GCIB自傾斜方θ π ^ 視圖。在圖】中，較m處理表面上之狀態的 Τ較佳將由玻璃基板1之法線N(因此為處理Examples include SF6, nf3, CHF3, CF4, Γ C 4 , C3F8, C4F6, SiF4 and COF2. These gases can be used singly or in combination. By using the accelerating voltage to be applied to the accelerating electrode to control "Μ keV, even in the execution of the GCIB etching for the finishing treatment of the surface of the table; the condition of the source gas used by the known σ ^ 卜 processing surface The amount of etching on the upper surface is also low enough, and the worries present on the treated surface can be removed to substantially eliminate the treated surface. In the case of accelerating voltage, the "* 疋 ' 、 、 于 于 于 于 于 于 于 于 于 于 于 于 于When the gas family collides with the treated surface, the impurities on the moving surface are considered to be large and small, so that the treatment is present in a small size and cannot be removed. Specifically, the impurity 屮m' having a size of 1 μm to 2 μη is not removed. When the accelerating voltage exceeds 15 keV, the kinetic energy is large when the gas, .m chaotic body set collides with the treated surface. Therefore, the treatment of the fine impurities on the surface of the surface of the surface of the moon b + @ / 乍 比 比 移除 移除 移除 @ @ + + + @ + + @ @ @ + + @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ Under the condition of the place, the part of the main surface of the Lu god remains unetched, so that the heart and the surface have been treated by washing or similar to the surface of the μ ^ π fly to remove the miscellaneous and convex defects. Impurity) Accelerated electricity is better than 5keV to Ι〇Μ. In the case of the impurity removal method of the present invention, in the treatment of 矣β, Yin, in order to perform coffee sculpt on the low-etching bB, C〇2 Ν〇 surface and surface, using a gas selected from 〇2, a gas 2 Source ^ such as 'call and ^. At least one of the surface collisions, complex: GCW etching. When the gaseous substance reacts with the treatment, and the surface is treated as I30467.doc 200902461 and the weakly used GC_etched sheet is used as the source gas, the impurities present on the treated surface can be removed. Without substantially treating the treated surface. In the second embodiment of the impurity removing method of the present invention, the accelerating electric power for applying the gas substance having the extremely weak etching action to the accelerating electrode is not particularly limited. However, it is preferable that the acceleration voltage is 15 W or more from the viewpoint of removing the impurities existing on the treated surface without substantially treating the treated surface. The acceleration voltage is more preferably 20 keV or more, and further preferably 3 〇W or more. When the acceleration voltage is less than 15 keV, when the gas clusters collide with the treated surface, the kinetic energy is small, and the & Depending on the size, there is a possibility that the impurity f existing on the processing surface cannot be removed. However, even when the accelerating voltage is less than 15 keV, the impurities present on the treated surface can be removed by adjusting the size, dose, irradiation time, and the like. According to the foregoing first embodiment and the second embodiment of the impurity removing method of the present invention, since gCIB* is performed on the processing surface under low-touch conditions, impurities existing on the processing surface can be removed without being substantially processed. Handle the surface. The low etching condition as referred to herein is preferably a condition in which the etching amount is 20 nm or less, and more preferably a condition in which the amount of money is below the (7) plane. In the first embodiment and the third embodiment of the impurity shifting method of the present invention, the irradiation conditions (for example, cluster size, to be applied) can be appropriately selected depending on the kind of the source gas, the acceleration voltage applied to the accelerating electrode, and the like. To the ionization electrode of the GCIB etching apparatus to ionize the clustered ionization current and the dose of gCIB). Preferably, the GCIB etch is performed under conditions of a collector size of 2 or more. When the cluster size is 2 or more, since the larger gas clusters and the processing table are opposite to each other, it can be expected to enhance the removal of the surface of the human being due to multiple collision effects. The effect of the impurity on the cluster. The cluster size is preferably 3, _ or more, and particularly preferably 5, just above. In the first embodiment and the second embodiment of the invention, the impurity removal method preferably makes the GCIB self-tilt When the direction of illumination is irradiated to the field from the oblique direction, the GCIB can be expected to enhance the effect of impurities present on the treated surface due to the multi-person collision effect. 1 is a view showing the self-tilting θ π ^ view of the GCIB. In the figure, the Τ of the state on the m-treated surface is preferably the normal N of the glass substrate 1 (hence the processing)
表面10之法線Ν)盘将Λ^+S 待入射至處理表面1 〇之GCIB所形成之 =持3至60度。藉由保持㈣度以上，可預期歸:； 夕-人碰撞效應而增強移除存在於處理表面上之雜質之效 應。另-方面’當角0保持超出6〇度時，處理表面上之 GCIB之斑點形狀（sp〇tshape)變為顯著之橢圓形。因此， 當氣體簇集與慮4：^ 士 處理表面碰撞時，動能被分散，藉此移除存 在於處理表面上之雜f之效應被減小。又’由於處理表面 j之GCIB之斑點形狀變為顯著之撕圓形，所以存在在執 仃GCIB蝕刻之後處理表面之平坦度劣化的可能性。 ’且進―步較佳地保持角 30至60度。 在使GCIB自傾斜方向照射於處理表面上之狀況下，如 圖1中所3兄明’較佳在處理表面1G相對於水平 度面朝下之狀態下，使㈣以水平方向照射。根據此,； 形不僅歸因於多次碰撞效應而增強移除存在於處理表面 130467.doc -19- 200902461 上之雜質之效應，而且有可能防止已移除之雜質重新附著 於處理表面上。使處理表面10保持於相對於水平方向較佳 成10至60度，且更佳成30至60度面朝下的狀態。 本發明之處理方法（1)包括：藉 4贷啊之刖4雜質移 '于、> 移除玻璃基板表面上之雜f的步驟（此步驟在下文 中將稱為”雜質移除步驟，，）；及藉由選自由離子束姓刻、 Gem㈣、電漿_及奈㈣#所組成之群的處料法 來處理玻璃基板表面之步驟（此步驟在下文中將稱為 步驟”）。 在處理表面經預研磨以具有預定平坦度及表面粗縫度之 狀況下，在藉由本發明之前述雜質移除方法移除存在於處 理表面上的雜f之後，藉由選自由離子束㈣、GC職 刻、電漿韻刻及奈米磨姓所組成之群的處理方法來精處理 處理表面。 為了防止在雜質移除步驟之後新雜質附著於處理表面 上’較佳在同一腔室中執行雜質移除步驟及處理步驟，或 在以可輸送基板而無需自裝置卸下之方式並排置放之腔室 中執行雜質移除步驟及處理步驟。在於處理步驟中使用 GC職刻之狀況下’較佳在雜質移除步驟及處理步驟中 使用同一 GCIBI虫刻裝置。 在前述處理方法中，較佳使用Gcm蚀刻，此係因為表 面可經精處理以具有小表面粗趟度及極佳的平滑度。 在使用GCIB!虫刻之狀況下，可單獨或混合地使用諸如 SF6 Ar、〇2、n2、NF3、N2〇、CHF3、CF4、C2F6、 130467.doc •20· 200902461 C3F8、C4F6、Sif4及COF2之氣體作為來源氣體。在此等氣 體中，自當氣體簇集與處理表面碰撞時發生之化學反應之 觀點，SF6、NF3、CHF3、CF4、C2F6、C3F8、C4F6、SiF4 及COF2作為來源氣體為極佳的。尤其，由於蝕刻速率高且 增強處理節拍之原因，含有SF6或NF3之混合氣體（具體言 ' 之，SF6與02之混合氣體，SF6、Ar與02的混合氣體，NF3 • 與〇2之混合氣體，NF3、Ar與〇2之混合氣體，NF3與N22 混合氣體及NF3、Ar與N2的混合氣體）為較佳的。在此混合 f κ 氣體中，雖然各別組份之適宜混合比率隨著諸如照射條件 之條件而改變，但以下混合比率為較佳的。 SF6/O2 = 0· 1%至 5%/95%至 99.9%(SF6與 02之混合氣體） SF6/Ar/O2 = 0.1% 至 5%/9.9% 至 49.9%/50% 至 90%(SF6、Ar 與02之混合氣體） NF3/O2=0.1%至 5%/95%至 99.9%(NF3與 02之混合氣體） NF3/Ar/O2=0.1% 至 5%/9.9% 至 49.9%/50% 至 90%(NF3、Ar 4. 與Ο 2之混合氣體） NF3/N2=0.1 % 至 5 %/9 5 % 至 99 _9%(NF3 與 N2 之混合氣體） NF3/Ar/N2 = 0.1% 至 5%/9.9% 至 49.9%/50% 至 90%(NF3、Ar * 與川之混合氣體） - 在此等混合氣體中，SF6與02之混合氣體，SF6、Ar與02 之混合氣體，NF3與02之混合氣體及NF3、Ar與02之混合 氣體為較佳的。 可根據來源氣體之種類、處理表面之表面性質、精處理 之用途等來適當選擇照射條件（例如，簇集大小、待施加 130467.doc -21 - 200902461 至GCIB㈣裝置之離子化電極以離子化簇集之離子化電 流及㈣的劑量)。舉例而言，在為了在初步處理之後改 善處理表面之平坦度而執行精處理之狀況下，待施加至加 速電極之加速電壓較佳超出15 keV;且為了改善處理表面 之平坦度而不使表面粗糖度過度劣化，加速電塵較佳超出 15 keV而在30 keV以下。 又，在處理步驟巾，在使用GCIB儀刻之狀況下，有必 要在處理表面上掃描GCIB。作為掃描gcib之方法，已知 光栅掃描及螺旋掃描，且可使用此等方法中之任—者。 本發月之處理方法（2)包括：量測玻璃基板表面之平坦 度之步驟（此步驟在下文中將稱為"平坦度量測步驟藉 由本發明之前述雜質移除方法移除處理表面上的雜質之: 驟（此步驟在下文中將稱為"雜質移除步驟„); &藉由選自 由離子束蝕刻、GCIB蝕刻、電漿蝕刻及奈米磨蝕所組成 之群的處理方法來處理處理表面之步驟（此步驟在下文中The normal 表面 of the surface 10) is 3^+S to be incident on the treated surface 1 〇 GCIB formed = 3 to 60 degrees. By maintaining (four) degrees or more, it is expected that the effect of removing the impurities present on the treated surface is enhanced by the eve-human collision effect. On the other hand, when the angle 0 is kept beyond 6 degrees, the spot shape (sp〇tshape) of the GCIB on the treated surface becomes a remarkable elliptical shape. Therefore, when the gas cluster collides with the surface of the treatment surface, the kinetic energy is dispersed, whereby the effect of removing the impurity f existing on the treated surface is reduced. Further, since the spot shape of the GCIB of the treated surface j becomes a significant tear round shape, there is a possibility that the flatness of the treated surface deteriorates after the GCIB etching is performed. And the step is preferably maintained at an angle of 30 to 60 degrees. In the case where the GCIB is irradiated onto the treatment surface from the oblique direction, as shown in Fig. 1, it is preferable to irradiate (4) in a horizontal direction in a state where the treatment surface 1G faces downward with respect to the horizontal surface. According to this, the shape is enhanced not only by the effect of multiple collisions but also by the removal of the impurities present on the treated surface 130467.doc -19-200902461, and it is possible to prevent the removed impurities from reattaching to the treated surface. The treatment surface 10 is maintained in a state of preferably 10 to 60 degrees with respect to the horizontal direction, and more preferably 30 to 60 degrees face down. The processing method (1) of the present invention comprises the steps of: removing the impurities on the surface of the glass substrate by removing the impurities from the surface of the glass substrate (this step will hereinafter be referred to as "the impurity removal step," And a step of treating the surface of the glass substrate by a method selected from the group consisting of ion beam surname, Gem (four), plasma _, and nai (four) # (this step will hereinafter be referred to as a step). In the case where the treated surface is pre-ground to have a predetermined flatness and a rough surface degree, after removing the impurity f present on the treated surface by the aforementioned impurity removing method of the present invention, by selecting from the ion beam (four), The processing method of the GC group, the plasma rhyme, and the group consisting of the nanometer's surname is used to finish the surface treatment. In order to prevent new impurities from adhering to the processing surface after the impurity removing step, it is preferable to perform the impurity removing step and the processing step in the same chamber, or to arrange and dispose in a manner that the substrate can be transported without being removed by the device. An impurity removal step and a processing step are performed in the chamber. The same GCIBI insect engraving device is preferably used in the impurity removal step and the processing step in the case where the GC is used in the processing step. Among the foregoing treatment methods, Gcm etching is preferably used because the surface can be finished to have a small surface roughness and excellent smoothness. In the case of using GCIB! insects, such as SF6 Ar, 〇2, n2, NF3, N2〇, CHF3, CF4, C2F6, 130467.doc • 20· 200902461 C3F8, C4F6, Sif4 and COF2 can be used singly or in combination. The gas acts as a source gas. Among these gases, SF6, NF3, CHF3, CF4, C2F6, C3F8, C4F6, SiF4 and COF2 are excellent as source gases from the viewpoint of chemical reactions occurring when gas clusters collide with the treated surface. In particular, due to the high etching rate and enhanced processing tempo, a mixed gas containing SF6 or NF3 (specifically, a mixed gas of SF6 and 02, a mixed gas of SF6, Ar and 02, a mixed gas of NF3 and 〇2) NF3, a mixed gas of Ar and 〇2, a mixed gas of NF3 and N22, and a mixed gas of NF3, Ar and N2 are preferred. In the mixed f κ gas, although the appropriate mixing ratio of the respective components changes depending on conditions such as irradiation conditions, the following mixing ratio is preferable. SF6/O2 = 0·1% to 5%/95% to 99.9% (mixture of SF6 and 02) SF6/Ar/O2 = 0.1% to 5%/9.9% to 49.9%/50% to 90% (SF6 , mixed gas of Ar and 02) NF3/O2=0.1% to 5%/95% to 99.9% (mixture of NF3 and 02) NF3/Ar/O2=0.1% to 5%/9.9% to 49.9%/50 % to 90% (mixture of NF3, Ar 4. and Ο 2) NF3/N2 = 0.1 % to 5% / 9 5 % to 99 _9% (mixture of NF3 and N2) NF3/Ar/N2 = 0.1% To 5%/9.9% to 49.9%/50% to 90% (NF3, mixed gas of Ar* and Chuan) - a mixed gas of SF6 and 02, a mixed gas of SF6, Ar and 02 in these mixed gases, A mixed gas of NF3 and 02 and a mixed gas of NF3, Ar and 02 are preferred. The irradiation conditions can be appropriately selected depending on the kind of the source gas, the surface property of the treated surface, the use of the finishing treatment, etc. (for example, the cluster size, the ionization electrode to be applied to the 130467.doc -21 - 200902461 to GCIB (4) device to ionize the cluster Set the ionization current and (four) dose). For example, in the case where the finishing treatment is performed in order to improve the flatness of the treated surface after the preliminary treatment, the acceleration voltage to be applied to the accelerating electrode preferably exceeds 15 keV; and in order to improve the flatness of the treated surface without making the surface The coarse sugar content is excessively deteriorated, and the accelerated electric dust is preferably more than 15 keV and less than 30 keV. Further, in the processing step, it is necessary to scan the GCIB on the processing surface in the case of using the GCIB. As a method of scanning gcib, raster scanning and helical scanning are known, and any of these methods can be used. The treatment method (2) of the present month includes the step of measuring the flatness of the surface of the glass substrate (this step will hereinafter be referred to as " flatness measurement step by removing the treatment surface by the aforementioned impurity removal method of the present invention Impurity: This step (hereinafter referred to as " impurity removal step „); & by a treatment method selected from the group consisting of ion beam etching, GCIB etching, plasma etching, and nano-abrasive The step of processing the surface (this step is below)
將％為’處理步驟"），其中，在處理步驟中，基於自平坦度 置測步驟獲得之結果針對處理表面之每—處設定處理表面 的處理條件。 為了處理玻璃基板之處理表面（例如，Euvl用遮罩之 玻璃基板的處理表面）而藉由離子束蝕刻、gcib蝕刻、電 漿蝕刻或奈米磨蝕來執行初步處理及精處理之狀況下，有 時可能在初步處理之後有部分波紋存在於處理表面上。本 斤h及之波紋意謂在存在於處理表面上之循環性不規 則丨生中具有5至30 mm之循環的不規則性。 130467.doc -22- 200902461 精由精4理難以移㉟此波紋以使處理表面上具有所期望 之平坦度，也可能存在初步處理中所產生之波紋在精處理 期間成長為更大波紋之狀況。 本發明之處理方法⑺為一種方法，其中此類在初步處 理之後產生於處理表面上之波紋被移除，且處理表面被精 處理為具有極佳平坦度的表面。 在本發明之處理方丰& ()中為了根據由平坦度量 + 驟所獲得，結果針對處理表面之每一處設定處理表面之處 理條件，較佳為在處理步驟之前執行平坦度量測步驟。平 =量，驟可在雜質移除步驟之後執行。然而 雜質移除步驟之後有新雜質附著於處理表面上，平” ί 測步驟在雜質移除步驟之前執行為宜。 ^ ^為了防止在雜f移除步驟之後新雜質附著於處理表 ^、，較佳在同—腔室中執行㈣移除步驟及處理步驟， $以可輸送基板而無需自裝置 宫φ劫#；ΙΓ<万式並排置放之腔 至中執仃雜質移除步驟及處理步驟 GCIB蝕刻之肤、、兄丁 > 隹於處理步驟中使用 ，tm / ，父佳在雜質移除步驟及處理步驟中% is the 'processing step"), wherein, in the processing step, the processing conditions of the processing surface are set for each of the processing surfaces based on the result obtained by the self-flatness detecting step. In order to process the treated surface of the glass substrate (for example, the processing surface of the glass substrate of the Uuvl mask), the preliminary processing and the fine processing are performed by ion beam etching, gcib etching, plasma etching, or nano abrasion. It is possible that some of the ripples are present on the treated surface after the initial treatment. The corrugation of the pounds means that there is an irregularity of a cycle of 5 to 30 mm in the cyclic irregularity existing on the treated surface. 130467.doc -22- 200902461 It is difficult to move 35 corrugations to have the desired flatness on the treated surface, and there may be a situation in which the ripple generated in the preliminary treatment grows into a larger corrugation during the finishing process. . The treatment method (7) of the present invention is a method in which the corrugations generated on the treatment surface after the preliminary treatment are removed, and the treatment surface is refined into a surface having excellent flatness. In the processing of the present invention, in order to obtain the processing conditions of the processing surface for each of the processing surfaces, it is preferred to perform the flat measurement step before the processing step in order to obtain the processing conditions for the processing surface according to the flat metric + step. . The level = amount can be performed after the impurity removal step. However, after the impurity removal step, new impurities are attached to the treatment surface, and the flat measurement step is performed before the impurity removal step. ^ ^ In order to prevent new impurities from adhering to the treatment table after the impurity f removal step, Preferably, the (four) removal step and the processing step are performed in the same chamber, and the substrate can be transported without the need for self-contained ΙΓ 劫 ΙΓ ΙΓ ΙΓ ΙΓ ΙΓ 万 万 万 万 万 并 至 至 至 至 至 至 至 至 至 至 至 仃 仃 仃 仃 仃 仃 仃 仃 仃GCIB etched skin, broth, 隹 used in the processing step, tm / , parent in the impurity removal step and processing step
使用冋一GCIB蝕刻裝置。 灭評T 在平坦度量測步驟令1 度(亦即，高度旬。因此，自平”:：一處中之平坦 變為展干# 目十坦度®測步驟獲得之結果 夂局展不處理表面之每一處 下文中將稱為，，平坦度圖”。)-度差的平坦度圖(此在 處理表面之每—虛由* ,丁 平坦度量測器件進二=而度可(例如)藉由雷射干涉型 不應解釋為本發明受此 130467.doc -23- 200902461 限制。可使用量測結果而製備平坦度圖，該量測結果係藉 2使用雷射位移量規、超聲波位移量規或接觸型位移量規 量測處理表面之每一處中的高度差而獲得。 在本發明之處理方法（2)中，在執行平坦度量測步驟及 ㈣移除步驟之後，基於自平坦度量測步驟獲得之結果為 處理表面中之每一處設定處理表面的處理條件。 如先前所描述’自平坦度量測步驟獲得之結果變為平坦 〇 度圖在將為-維平面形狀之處理表面之座標定義為(X, y)之狀況下，平坦度圖可藉由s(x，幻化㈨來表達。藉由 T(x，yKmin)來表達處理時間。在將處理速率定義為γ bm/min)之狀況下，此等參數之間的關係藉由以下等式表 達：Use a GCIB etching device. Destroy T in the flat measurement step to make 1 degree (that is, the height of the tenth. Therefore, self-leveling::: the flatness in one place becomes the dry-drying #目十坦度® test step results obtained Each of the processing surfaces will be referred to hereinafter as the flatness map ".) - the flatness map of the degree difference (this is in the processing surface - the virtual factor *, the flat flat measuring device is in the second = (For example) by laser interference type, it should not be construed that the invention is limited by this 130467.doc -23- 200902461. The flatness map can be prepared using the measurement results, which is based on the use of a laser displacement gauge. Obtaining a height difference in each of the surfaces of the ultrasonic displacement gauge or the contact displacement gauge. In the processing method (2) of the present invention, after performing the flat measurement step and the (4) removal step The result of the self-flattening measurement step is the processing condition for setting the processing surface for each of the processing surfaces. As described previously, the result obtained by the self-flattening measurement step becomes a flatness graph which will be - The coordinates of the treated surface of the dimension plane are defined as (X, y) The flatness map can be expressed by s(x, illusion (9). The processing time is expressed by T(x, yKmin). Under the condition that the processing rate is defined as γ bm/min), between these parameters The relationship is expressed by the following equation:
T(x, y) = S (x, y)/Y 相應地，在基於自平坦度量測步驟獲得之結果來為處理 j面中之每-處設定處理表面之處理條件之狀況下，根據 ί, 前述等式為處理表面中之每一處設定處理條件（具體言 之，處理時間ρ σ 在處理步射，在制伴有在處理表面上之射束照射之 •方法之狀況下，具體言之，在使用離子束I虫刻、GC叫虫 . 安]或電漿蝕刻之狀況下，可基於自平坦度量測步驟獲得之 、、、口果為處理表面中之每一處設定處理表面之處理條件。下 文具體描述用於此情形之設定程序。 1在執行此設定程序之狀況下，使用自平坦度量測步驟獲 付之結果才曰疋存在於處理表面上之波紋的寬度。如本文中 130467.doc -24- 200902461 提及之波紋寬度意謂循環地存在於處理 中之凹陷部分或凸狀部分的長度。因此，波紋寬 波紋寬度之循環的1/2。在具有不同循環之複數個波紋脫 離之狀況下，採用具有最小循環之波紋之寬度作為存在於 處理表面上的波紋之寬度。 如先前所描述’自平坦度量測步驟獲得之量測結果為展 示處理表面中之每一處中之高度差的平坦度圖。因此，有 可能自平坦度圖容易地指定存在於處理表面上的波紋寬 度。 基於如在前述程序中指定之波紋寬度由具有不大於波紋 寬度之射束直徑的射束執行離子束蝕刻、GCIB蝕刻或電 漿蝕刻。如本文中提及之射束直徑係基於半高寬（fwhm) 值。在此說明書中，當提及射束直徑時’其意謂射束直徑 的FWHM值。在處理步驟中，更佳使用具有不大於波紋寬 度之1/2之射束直徑的射束。藉由使用具有不大於波紋寬 度之射束直徑的射束，有可能照射射束，㈣集中於存在 於處理表面上的波紋上且有效地移除波紋。 在處理步驟中，當使用伴有在處理表面上之射束照射之 方法打，亦即，在使用離子束蝕刻、GCIB蝕刻或電漿蝕 刻之狀況下，有必要在處理表面上掃描射束。此係因為為 為处里表面中之母一處設定處理表面的處理條件，需要 使得由射束一次照射之範圍儘可能小。詳言之，在使用具 有不大於波紋寬度之射束直徑的射束之狀況下，有必要以 射束掃描處理表面°作為以射束進行掃描之方法，已知光 130467.doc -25- 200902461 柵掃描及螺旋掃描’且可使用此等方法中的任—者。 在如述處理方法中，較佳梓用g r T R +1 ΙΒ敍刻，此係因為表 π、，丄處理以具有小的表面粗糙度及極佳平滑度。 :使用gCIB银刻之狀況下，來源氣體及照射條件盘關 :本發明之處理方法⑴所描述之彼等來源氣體及照射 相同。 / 丁 、當執行根據本發明之處理方法⑴或⑺之處理步驟時， 視處理表面之性f或射束之照射條件*定，可能存在處理 表面之表面粗糙度稍微劣化的狀況。又，可能存在以下狀 况.甚至當在前述處理步驟中可達成所要平坦度時，視玻 璃基板之規格而定，表面不可經處理以具有所要表面粗輪 度。由於該原因，較佳在前述處理步驟（在下文中稱為，，第 處理步驟）之後’為了改善處理表面之表面粗縫度而執 行第二處理步驟。 —在第二處理步驟中，可使用GCIB蝕刻。在該狀況下， 藉由自待用於雜質移除方法中之GCIB蝕刻及待用於第一 處理步驟中之GCIB*刻中所使用之彼等照射條件改變照 射條件（諸如，來源氣體、離子化電流及加速電壓）而執行 GCIB蝕刻。具體言之，在一照射條件下執行蝕刻， 使得蝕刻里低於待用於第一處理步驟中之GdB蝕刻中的 蝕刻量。與待用於第一處理步驟中之GCIB蝕刻相比較， 使用較低離子化電流或較低加速電壓在更溫和條件下執行 GCIB蝕刻。更具體言之，加速電壓較佳為3 keV以上且小 於3〇 keV，且更佳為3 keV至20 keV。又，自當來源氣體 130467.doc -26- 200902461 體或使用〇2 體的混合氣 ’較佳使用 與處理表面碰撞時之觀點，較佳單獨使用h氣 與至少一選自由Ar、CO及C〇2所組成之群之氣 體作為來源氣體，其難以引起化學反應。尤其 〇2與Ar之混合氣體。 又，在第二處理步驟中 .^ gi/cnl之低表面壓 力下執行稱為接觸研磨之使用研磨漿之機械研磨。在接 研磨中，將玻璃基板設定為插入於各自具備由非編織物、T(x, y) = S (x, y)/Y correspondingly, in the case of setting the processing conditions of the processing surface for each of the processing j planes based on the result obtained by the self-flattening measurement step, ί, the foregoing equation sets the processing conditions for each of the processing surfaces (specifically, the processing time ρ σ is in the processing step, in the case of the method of manufacturing the beam irradiation on the processing surface, In other words, in the case of using ion beam I insect, GC, or plasma etching, the processing can be based on the self-flatness measurement step, and the mouth is set for each of the processing surfaces. Processing conditions for the surface. The setting procedure for this case is specifically described below. 1 In the case where this setting procedure is performed, the result obtained by the self-flattening measurement step is the width of the corrugation present on the processing surface. The corrugation width as referred to herein by 130467.doc -24-200902461 means the length of the concave portion or the convex portion which is cyclically present in the treatment. Therefore, the width of the corrugation width is 1/2 of the cycle. Multiple ripples In this case, the width of the corrugation with the smallest cycle is used as the width of the corrugations present on the treated surface. The measurement obtained from the flatness measurement step as described previously is to show the height in each of the treated surfaces. Poor flatness map. Therefore, it is possible to easily specify the width of the corrugation present on the processing surface from the flatness map. The corrugation width based on the beam diameter specified in the foregoing procedure is performed by a beam having a beam diameter not greater than the corrugation width. Ion beam etching, GCIB etching, or plasma etching. The beam diameter as referred to herein is based on a full width at half maximum (fwhm) value. In this specification, when referring to the beam diameter, it means the beam diameter. FWHM value. In the processing step, it is more preferable to use a beam having a beam diameter of not more than 1/2 of the width of the corrugation. By using a beam having a beam diameter not larger than the width of the corrugation, it is possible to illuminate the beam, (d) focusing on the corrugations present on the treated surface and effectively removing the corrugations. In the processing step, when using the method of beam irradiation accompanied on the treated surface, that is, In the case of ion beam etching, GCIB etching or plasma etching, it is necessary to scan the beam on the processing surface. This is because the processing conditions for setting the processing surface for the mother in the inner surface need to be made by the beam. The range of one irradiation is as small as possible. In particular, in the case of using a beam having a beam diameter not larger than the width of the corrugation, it is necessary to scan the surface as a beam scanning method. Light 130467.doc -25- 200902461 grid scanning and helical scanning 'and any of these methods can be used. In the processing method as described, it is better to use gr TR +1 ΙΒ ,, this is because the table π , 丄 treatment to have a small surface roughness and excellent smoothness.: Under the condition of gCIB silver engraving, the source gas and the irradiation condition are closed: the source gases and the irradiation described in the treatment method (1) of the present invention are the same . When the processing steps of the treatment method (1) or (7) according to the present invention are carried out, depending on the nature of the treatment surface f or the irradiation condition of the beam, there may be a case where the surface roughness of the treatment surface is slightly deteriorated. Also, the following conditions may exist. Even when the desired flatness can be achieved in the foregoing processing steps, depending on the specifications of the glass substrate, the surface may not be treated to have a desired surface coarseness. For this reason, it is preferred to perform the second processing step in order to improve the surface roughness of the treated surface after the aforementioned processing steps (hereinafter referred to as the first processing step). - In the second processing step, GCIB etching can be used. In this case, the irradiation conditions (such as source gas, ion) are changed by the GCIB etching to be used in the impurity removal method and the illumination conditions to be used in the GCIB* in the first processing step. The electrochemical current and the accelerating voltage are performed to perform GCIB etching. Specifically, the etching is performed under an irradiation condition so that the etching amount is lower than the etching amount to be used in the GdB etching in the first processing step. The GCIB etch is performed under milder conditions using a lower ionization current or a lower accelerating voltage than the GCIB etch to be used in the first processing step. More specifically, the accelerating voltage is preferably 3 keV or more and less than 3 〇 keV, and more preferably 3 keV to 20 keV. Further, since the source gas 130467.doc -26-200902461 body or the mixture of the 〇2 body is preferably used in view of collision with the treated surface, it is preferred to use the gas alone and at least one selected from the group consisting of Ar, CO and C. The gas of the group consisting of 〇2 is a source gas, and it is difficult to cause a chemical reaction. Especially a mixture of 〇2 and Ar. Further, in the second processing step, mechanical polishing using a slurry called contact grinding is performed under a low surface pressure of ?gi/cnl. In the polishing, the glass substrate is set to be inserted into each of the non-woven fabrics,
編織=或其類似物製成的研磨襯塾之研磨板之間，且研磨 板抵靠玻璃基板相對旋轉同時饋送經調整以具有預定性質 之⑽，藉此在160 gfW之表㈣力下對處理表面進 行研磨處理。 作為研磨襯墊，例如，由Kaneb0, Ltd,製造之 beLLATRIXK7512為可㈣。作為研㈣，較佳使用含膠 狀矽石之研磨漿；且更較佳使用含有具有5“喊下之平 均初級粒徑之膠狀⑦石及水且經調整以具有纽5至*範圍 内的PH值之研磨漿。研磨之表面壓力為1至60 gf/cm2。當 表面壓力超出6〇 gf/em2時，歸因於在基板表面或其類似物 上產生擦痕而不可能將處理表面處理至所要表面粗輪度。 又，存在=磨板之旋轉負載變大之可能性。當表面壓力小 ；g m 處理钯費長的時間週期，且因此此並非實踐 勺又菖表面屢力小於30 gf/cm2時，處理花費長 的日π間週期。因此，較佳地，在3()至Μ抑之表面麼力 处理至某程度之後’在1至3G gf/em2之表面壓力下對表面 進行精處理。 I30467.doc -27- 200902461 膠狀矽石之平均初級粒徑較佳小於2〇 nm，更佳小於 15nm且尤佳小於10 nm。當膠狀矽石之平均初級粒徑超出 50 時’難以處王里處理纟面以具有所要表面粗糙度。 又，自仔細管理粒徑之觀點，需要膠狀石夕石儘可能不含藉 由初級顆粒之凝結而形成的次級顆粒。在膠狀矽石含有次 級顆粒之狀況下，次級顆粒之平均粒徑較佳在川 下。如本文中提及之膠狀石夕石之粒徑為藉由掃描電子顯微 鏡（SEM)在^至⑽心倍之放大倍率下量測影像而獲得的 粒徑。 研磨漿中之膠狀矽石之含量以質量計較佳為贈。至 3㈣。當研磨漿中之膠狀石夕石之含量以f量計小於1〇% 時，存在研磨效率可能變差之可能性，藉此不能達到經濟 之研磨。另一方面，當膠狀石夕石之含量以質量計超出3〇% 時’由於膠狀矽石之使用量增加’自成本及洗滌能力之觀 點，存在引起問題的可能性。研磨激中之膠狀矽石之含量 更佳為以質量物至25% ’且尤佳為以質量計18%至 22%。 當使得研磨漿之阳值在前述酸性範圍内時，亦即，使得 PH值在0.5至4之範圍内’有可能使處理表面經受化學及機 械研磨處理’藉此達成具有良好平滑度之處理表面的有效 研，處理。亦即’藉由研磨聚中之酸來軟化處理表面之凸 狀部分’且因此，凸狀部分可藉由機械研磨容易地移除。 二凊开7 "^僅增強處理效率，而且已藉由研磨處理移 破璃廢棄物被軟化，且因此防止歸因於玻璃廢棄物 130467.doc -28- 200902461 或其類似物產生新損害。當研磨漿之pH值小於0.5時，存 在在待用於接觸研磨之研磨機中產生腐I虫之可能性。自研 磨聚之處置性質之觀點，pH值較佳為1以上。為了獲得足 夠之化學研磨處理效應，pH值較佳在4以下，且尤佳在I; 至2.5之範圍内。 研磨漿之pH值調整可藉由單獨添加無機酸或有機酸或兩 者之組合而達成。可使用之無機酸之實例包括硝酸、硫 酸、鹽酸、過氯酸及磷酸。在此等無機酸中，鑒於處置之 谷易性，硝酸為較佳的。又，有機酸之實例包括草酸及檸 檬酸。 作為待用於研磨漿之水，較佳使用純水或超純水（已自 。亥水移除雜質）。亦即，實質上每爪乙具有不多於—個具有 0.1 μιη以上之最大大小（如藉由使用雷射光或其類似物之光 散射杈式所量測）的精細顆粒之純水或超純水為較佳的。 當每mL併入一個以上雜質，則無關於材料品質或形狀， 存在在處理表面上形成表面缺陷（諸如，擦痕及凹坑）的可 能性。純水或超純水中之雜質可藉由（例如）使用薄膜過濾 器之過濾或超過濾而移除，但不應解釋為雜質移除方法受 此限制。 在如藉由本發明之處理方法（1)或（2)處理之玻璃基板 中，處理表面具有極佳平坦度及表面粗糙度；處理之後的 處理表面之平坦度在50 nm以下；且在處理表面上不存在 高度超出1.5 nm之玻璃的凸狀缺陷。處理之後的處理表面 之平坦度更佳在30 nm以下，且進一步較佳在2〇 nm以下。 130467.doc -29- 200902461 工業適用性 如藉由本發明之處理方法處理之玻璃基板可有利地作為 待用於半導體製造之曝光工具之光學系統中的光學器件， 尤其可有利地作為待用於具有45 nm以下線寬之半導體製 造之下一代曝光工具的光學系統中之光學器件，此係因為 處理表面具有極佳平坦度及表面粗糙度。此光學器件之特 定實例包括透鏡、繞射光柵、光學薄膜體及其複合體（例 如’透鏡、多透鏡、透鏡陣列、雙凸透鏡、複眼透鏡（fly_ eye lense)、非球面透鏡、鏡面、繞射光栅、二元光學器 件）、光罩及其複合體。 又’如藉由本發明之處理方法處理之玻璃基板可有利地 作為光罩及用於製造此光罩的遮罩基板（mask blank)，尤 其可有利地作為EUVL之反射型遮罩及用於製造此遮罩的 遮罩基板。 曝光工具之光源並不特定受限且可為能夠發出g射線（波 長：436 nm)或i射線（波長：365nm)之習知雷射。然而，較 短波長之光源（尤其具有25〇 nm以下的波長之光源）為較佳 的。此光源之特定實例包括KrF準分子雷射（波長：248 nm)、ArF準分子雷射（波長：193 nm)、f2雷射（波長：157 nm)及 EUV(波長：I3.5nm)。 雖然已詳細地且參看本發明之特定實施例描述本發明， 但熟習此項技術者將易瞭解，可在不背離本發明之精神及 範圍之情況下對本發明進行各種改變及修改。 本申請案係基於於2007年6月29日申請之日本專利申請 130467.doc •30- 200902461 案第2007-172274號，且其内容以引用之方式併入本文 中〇 【圖式簡單說明】 圖1為說明本發明之雜質移除方法中基板之處理表面與 GCIB之間的關係之示意圖。 【主要元件符號說明】. 1 基板 10 處理表面 N 玻璃基板之法線 Θ 角 130467.doc -31 -Between the abrasive plates of the ground lining made of braid = or the like, and the grinding plate is relatively rotated against the glass substrate while feeding (10) adjusted to have a predetermined property, thereby treating the treatment under the force of 160 gfW (four) The surface is ground. As the polishing pad, for example, beLLATRIXK7512 manufactured by Kaneb 0, Ltd. is (4). As research (4), it is preferred to use a slurry containing colloidal vermiculite; and more preferably, it contains a gelatinous 7 stone having a mean primary particle diameter of 5" and water and is adjusted to have a range of 5 to * The pH of the slurry. The surface pressure of the grinding is 1 to 60 gf/cm 2 . When the surface pressure exceeds 6 〇 gf / cm 2 , it is impossible to treat the surface due to scratches on the surface of the substrate or the like. Processing to the desired surface coarse rotation. Also, there is the possibility that the rotating load of the grinding plate becomes large. When the surface pressure is small; the time period during which gm is treated with palladium is long, and therefore this is not a practice spoon and the surface surface force is less than 30 At gf/cm2, the treatment takes a long period of π between the days. Therefore, preferably, after the surface treatment of 3() to the deuterium is to some extent, the surface is pressed at a surface pressure of 1 to 3 G gf/em2. Fine processing. I30467.doc -27- 200902461 The average primary particle size of colloidal vermiculite is preferably less than 2〇nm, more preferably less than 15nm and especially less than 10nm. When the average primary particle size of colloidal vermiculite exceeds 50 When it is difficult to handle the kneading surface in the king to have the desired surface roughness. From the viewpoint of finely managing the particle size, it is required that the colloidal stone is as far as possible free of secondary particles formed by the coagulation of the primary particles. The average particle size of the secondary particles in the case where the colloidal vermiculite contains secondary particles. Preferably, the particle size of the colloidal stone as described herein is a particle diameter obtained by measuring an image by a scanning electron microscope (SEM) at a magnification of (10) times the magnification. The content of the colloidal vermiculite is preferably given by mass. To 3 (4). When the content of the colloidal stone in the slurry is less than 1% by weight of f, there is a possibility that the grinding efficiency may be deteriorated. This does not achieve economic grinding. On the other hand, when the content of the colloidal stone is more than 3〇% by mass, 'the increase in the use amount of colloidal vermiculite' is problematic from the viewpoint of cost and washing ability. Possibility: the content of the colloidal vermiculite in the grinding is more preferably from 25% by mass and particularly preferably from 18% to 22% by mass. When the positive value of the slurry is within the aforementioned acidic range, That is, making the pH in the range of 0.5 to 4 'may make it possible The surface is subjected to chemical and mechanical grinding treatments, thereby achieving an effective grinding and treatment of the treated surface having good smoothness, that is, 'softening the convex portion of the surface by grinding the acid in the poly' and thus, the convex portion can be It is easily removed by mechanical grinding. The second opening 7 "^ only enhances the processing efficiency, and has been softened by the grinding process to remove the glass waste, and thus is prevented from being attributed to the glass waste 130467.doc -28- 200902461 or its analogues produce new damage. When the pH of the slurry is less than 0.5, there is a possibility of producing rot in the grinder to be used for contact grinding. From the viewpoint of the nature of the treatment of the grinding, the pH is higher. Good for 1 or more. In order to obtain a sufficient chemical polishing effect, the pH is preferably 4 or less, and particularly preferably in the range of I; to 2.5. The pH adjustment of the slurry can be achieved by adding a mineral acid or an organic acid alone or a combination of the two. Examples of inorganic acids which can be used include nitric acid, sulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid. Among these inorganic acids, nitric acid is preferred in view of the suitability of the treatment. Further, examples of the organic acid include oxalic acid and citric acid. As the water to be used for the slurry, it is preferred to use pure water or ultrapure water (which has been removed from the water). That is, substantially no more than one pure water or ultrapure of fine particles having a maximum size of 0.1 μm or more (measured by light scattering 雷 using laser light or the like) per claw B Water is preferred. When more than one impurity is incorporated per mL, there is a possibility that surface defects such as scratches and pits are formed on the treated surface regardless of the material quality or shape. Impurities in pure water or ultrapure water can be removed by, for example, filtration using a membrane filter or ultrafiltration, but should not be construed as limiting the method of impurity removal. In the glass substrate treated by the treatment method (1) or (2) of the present invention, the treated surface has excellent flatness and surface roughness; the flatness of the treated surface after the treatment is below 50 nm; There are no convex defects on the glass that exceed the height of 1.5 nm. The flatness of the treated surface after the treatment is more preferably 30 nm or less, and further preferably 2 μm or less. 130467.doc -29- 200902461 Industrial Applicability The glass substrate treated by the treatment method of the present invention can be advantageously used as an optical device in an optical system to be used for an exposure tool for semiconductor manufacturing, and is particularly advantageously used as having Optical devices in the optical system of the next-generation exposure tools manufactured by semiconductors with line widths below 45 nm, because of the excellent flatness and surface roughness of the treated surface. Specific examples of such optical devices include lenses, diffraction gratings, optical film bodies, and composites thereof (eg, 'lenses, multiple lenses, lens arrays, lenticular lenses, fly_eye lenses, aspherical lenses, mirrors, diffractions Gratings, binary optics), reticle and composites thereof. Further, the glass substrate treated by the treatment method of the present invention can be advantageously used as a mask and a mask blank for manufacturing the mask, and can be advantageously used as a reflection mask of EUVL and for manufacturing. The mask substrate of this mask. The light source of the exposure tool is not particularly limited and may be a conventional laser capable of emitting g rays (wavelength: 436 nm) or i rays (wavelength: 365 nm). However, a light source of a shorter wavelength (especially a light source having a wavelength of 25 Å or less or less) is preferable. Specific examples of such a light source include KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), f2 laser (wavelength: 157 nm), and EUV (wavelength: I3.5 nm). Although the present invention has been described in detail and by reference to the preferred embodiments of the present invention, it will be understood that The present application is based on Japanese Patent Application No. 130, 467, filed on Jun. 29,,,,,,,,,,,,,,,,,,,,,,, 1 is a schematic view showing the relationship between the treated surface of the substrate and the GCIB in the impurity removing method of the present invention. [Description of main component symbols]. 1 Substrate 10 Treatment surface N Normal of glass substrate Θ Angle 130467.doc -31 -
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007172274 | 2007-06-29 |
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| US (1) | US20100101940A1 (en) |
| EP (1) | EP2170778A1 (en) |
| JP (1) | JP2009029691A (en) |
| KR (1) | KR20100032865A (en) |
| CN (1) | CN101687696A (en) |
| TW (1) | TW200902461A (en) |
| WO (1) | WO2009004852A1 (en) |
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| JP5169163B2 (en) | 2006-12-01 | 2013-03-27 | 旭硝子株式会社 | Method for finishing a pre-polished glass substrate surface |
| JP5470703B2 (en) * | 2007-12-27 | 2014-04-16 | 旭硝子株式会社 | EUVL optical member and surface treatment method thereof |
| JP5490563B2 (en) | 2010-02-19 | 2014-05-14 | 東京エレクトロン株式会社 | Substrate cleaning method and substrate cleaning apparatus |
| JP2011173184A (en) * | 2010-02-23 | 2011-09-08 | Tokyo Electron Ltd | Polishing method |
| JP5236687B2 (en) * | 2010-05-26 | 2013-07-17 | 兵庫県 | Surface treatment method and surface treatment apparatus |
| JP5776397B2 (en) | 2011-07-19 | 2015-09-09 | 東京エレクトロン株式会社 | Cleaning method, processing apparatus and storage medium |
| US8513138B2 (en) | 2011-09-01 | 2013-08-20 | Tel Epion Inc. | Gas cluster ion beam etching process for Si-containing and Ge-containing materials |
| US8512586B2 (en) * | 2011-09-01 | 2013-08-20 | Tel Epion Inc. | Gas cluster ion beam etching process for achieving target etch process metrics for multiple materials |
| US8557710B2 (en) | 2011-09-01 | 2013-10-15 | Tel Epion Inc. | Gas cluster ion beam etching process for metal-containing materials |
| US8722542B2 (en) | 2012-06-08 | 2014-05-13 | Tel Epion Inc. | Gas cluster ion beam process for opening conformal layer in a high aspect ratio contact via |
| US8728947B2 (en) | 2012-06-08 | 2014-05-20 | Tel Epion Inc. | Gas cluster ion beam process for opening conformal layer in a high aspect ratio contact via |
| CN105378898A (en) * | 2013-02-25 | 2016-03-02 | 艾克索乔纳斯公司 | Defect reduction in a substrate treatment method |
| US9209033B2 (en) | 2013-08-21 | 2015-12-08 | Tel Epion Inc. | GCIB etching method for adjusting fin height of finFET devices |
| CN106463342B (en) * | 2014-04-01 | 2020-04-03 | Ev 集团 E·索尔纳有限责任公司 | Method and device for treating a surface of a substrate |
| US20190275565A1 (en) * | 2018-03-06 | 2019-09-12 | GM Global Technology Operations LLC | Method of selectively removing a contaminant from an optical component |
| KR102305099B1 (en) * | 2020-11-19 | 2021-09-27 | 한국기초과학지원연구원 | Mixed gas cluster ion beam generator and mass spectrometer comprising the same |
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| US4278493A (en) * | 1980-04-28 | 1981-07-14 | International Business Machines Corporation | Method for cleaning surfaces by ion milling |
| US6368664B1 (en) * | 1999-05-03 | 2002-04-09 | Guardian Industries Corp. | Method of ion beam milling substrate prior to depositing diamond like carbon layer thereon |
| US6808606B2 (en) * | 1999-05-03 | 2004-10-26 | Guardian Industries Corp. | Method of manufacturing window using ion beam milling of glass substrate(s) |
| JP4207153B2 (en) * | 2002-07-31 | 2009-01-14 | 旭硝子株式会社 | Substrate polishing method and apparatus |
| JP4219718B2 (en) * | 2003-03-28 | 2009-02-04 | Ｈｏｙａ株式会社 | Manufacturing method of glass substrate for EUV mask blanks and manufacturing method of EUV mask blanks |
| JP4665443B2 (en) * | 2004-06-22 | 2011-04-06 | 旭硝子株式会社 | Glass substrate polishing method |
| WO2006082751A2 (en) * | 2005-02-02 | 2006-08-10 | Asahi Glass Company, Limited | Process for polishing glass substrate |
| JP4548319B2 (en) * | 2005-02-02 | 2010-09-22 | 旭硝子株式会社 | Glass substrate polishing method |
| KR20080017034A (en) * | 2005-06-14 | 2008-02-25 | 아사히 가라스 가부시키가이샤 | Method of finishing pre-polished glass substrate surface |
| JP4506689B2 (en) * | 2005-06-14 | 2010-07-21 | 旭硝子株式会社 | Method for finishing a pre-polished glass substrate surface |
| JP4997815B2 (en) * | 2006-04-12 | 2012-08-08 | 旭硝子株式会社 | Method for producing a highly flat and highly smooth glass substrate |
| JP5169163B2 (en) * | 2006-12-01 | 2013-03-27 | 旭硝子株式会社 | Method for finishing a pre-polished glass substrate surface |
-
2008
- 2008-04-11 TW TW097113328A patent/TW200902461A/en unknown
- 2008-04-11 CN CN200880022677A patent/CN101687696A/en active Pending
- 2008-04-11 KR KR1020097027326A patent/KR20100032865A/en not_active Application Discontinuation
- 2008-04-11 EP EP08740610A patent/EP2170778A1/en not_active Ceased
- 2008-04-11 WO PCT/JP2008/057553 patent/WO2009004852A1/en active Application Filing
- 2008-04-25 JP JP2008115127A patent/JP2009029691A/en not_active Withdrawn
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| EP2170778A1 (en) | 2010-04-07 |
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| US20100101940A1 (en) | 2010-04-29 |
| JP2009029691A (en) | 2009-02-12 |
| KR20100032865A (en) | 2010-03-26 |
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