TW200830034A

TW200830034A - Method of smoothing surface of substrate for EUV mask blank, and EUV mask blank obtained by the method

Info

Publication number: TW200830034A
Application number: TW96138350A
Authority: TW
Inventors: Mika Yokoyama; Yoshiaki Ikuta; Katsuhiro Matsumoto
Original assignee: Asahi Glass Co Ltd
Priority date: 2006-10-13
Filing date: 2007-10-12
Publication date: 2008-07-16
Also published as: WO2008047886A1

Abstract

The present invention is to provide a method of smoothing a surface of a substrate for an EUV mask blank, having concave defects such as pits or scratches. The present invention relates to a method of smoothing a surface of a substrate for a reflective mask blank for EUV lithography, comprising applying a solution containing a polysilazane compound to a substrate surface having concave defects, and heating and curing the applied solution to form a silica coating (a coating comprising SiO2 as a main skeleton), thereby smoothing the substrate surface having concave defects.

Description

200830034 九、發明說明：【發明所屬之技術領域】本發明係關於用於EUV(遠紫外線）微影之反射式光罩基底（該光罩基底在下文中稱為"EUV光罩基底"）用基板表面之平滑方法。更特定言之，本發明係關於EVU光罩基底用基板的具有凹缺陷之表面之平滑方法。本發明進一步係關於藉由平滑方法獲得之EUV光罩基底用基板及使用該基板之EUV光罩基底。【先前技術】藉由以反射膜及吸收層之順序在超拋光基板上形成該反射膜及該吸收層來製造用於EUV微影之光罩基底（下文稱為’’EUV光罩基底”）。該反射膜最通常為包含交替層壓之 Mo層及Si層的多層反射膜。若EUV光罩基底製造中所用之基板表面上存在微粗糙，則其會不利影響基板上所形成之反射膜及吸收層。舉例而言，若基板表面上存在微粗糙，則基板上所形成之多層反射膜之週期結構攝動，且若使用暴露裝置將光罩上之圖案轉移至Si晶圓上之感光有機膜（所謂之光阻膜），則所要圖案之一部分可能會有缺陷，或可能形成除所要圖案外之多餘圖案。歸因於基板上存在之微小凹面及凸面的多層反射膜之週期結構攝動稱為相缺陷，且此為嚴重問題。基板上不存在具有預定尺寸或更大尺寸之凹面及凸面為合乎需要的。非專利文獻1及2描述與EUV光罩及EUV光罩基底之缺陷 125722.doc 200830034 有關之要求，且與彼等缺陷有關之要求非常嚴格。非專利文獻1描述當基板上存在超過5〇 ηπΐ2缺陷時，在反射式塗層之結構中引起攝動，導致產生突出於以晶圓之抗蝕層上之非預期形狀之圖案，且不允許存在該等缺陷。非專利文獻1進步描述就突出於Si晶圓之抗飿層上之圖案的rms (均方根）粗糙度而言，需要基板之表面粗糙度小於〇15 nm 以防止線性邊緣之粗糙度增加。非專利文獻2描述微影中所用之塗有反射膜之主光罩上不允許存在超過25 nm 的缺陷。非專利文獻3描述基板上可能轉移多大尺寸程度之缺卩曰。非專利文獻3描述相缺陷可能會改變所印刷影像之線覓。其中進一步描述具有高度為2 11111且FWHM(半高全寬）為60 nm之表面凸塊的相缺陷具有如下尺寸，該尺寸為此尺寸之相缺陷是否可轉移且引起線寬之不能允許之變化（該變化為35 nm線寬之20%(光罩上線寬為14〇 nm))的邊界條件。在基板表面上所存在之微粗糙中，諸如外來物質（顆粒）或纖維之凸缺陷可藉由使用氫氟酸或氨水之習知濕式清潔法、刷式清潔、精密拋光及其類似方法來移除。然而，諸如坑或刮痕之凹缺陷不可藉由彼等方法來移除。此外’當塗敷❹氫I酸或氨水之濕式清料時，需要在基板表面略微塗敷餘刻以藉由起離（Hft〇ff)系統自基板移除凸缺陷，且基板表面上可能會因此產生新的凹缺陷。即使在使用刷式清潔以移除凸缺陷時，基板表面上亦可能會產生新的凹缺陷。 125722.doc 200830034 非專利文獻 1 : SEMI，P37-1102 (2002)，"Specification for extreme ultraviolet lithography mask substrates*' 非專利文獻2 : SEMI，P38-1102 (2002)，"Specification for absorbing film stacks and multilayers on extreme ultraviolet lithography mask blanks11 非專利文獻3 : SPIE，第4889卷，Alan Stivers等人，第 408-417 頁（2002)，’’Evaluation of the Capability of a200830034 IX. Description of the Invention: [Technical Field] The present invention relates to a reflective reticle substrate for EUV (extreme ultraviolet ray) lithography (this reticle substrate is hereinafter referred to as "EUV reticle substrate") A smoothing method using the surface of the substrate. More specifically, the present invention relates to a method of smoothing a surface having a concave defect of a substrate for an EVU photomask substrate. The present invention further relates to a substrate for an EUV reticle substrate obtained by a smoothing method and an EUV reticle substrate using the substrate. [Prior Art] A reticle substrate for EUV lithography (hereinafter referred to as ''EUV reticle substrate') is manufactured by forming the reflective film and the absorbing layer on an ultra-polished substrate in the order of a reflective film and an absorbing layer. The reflective film is most commonly a multilayer reflective film comprising alternately laminated Mo layers and Si layers. If there is micro-roughness on the surface of the substrate used in the manufacture of the EUV mask substrate, it may adversely affect the reflective film formed on the substrate. And an absorbing layer. For example, if there is micro-roughness on the surface of the substrate, the periodic structure of the multilayer reflective film formed on the substrate is perturbed, and if the pattern on the reticle is transferred to the sensitization on the Si wafer by using an exposure device An organic film (so-called photoresist film) may have defects in one part of the desired pattern, or may form an unnecessary pattern other than the desired pattern. The periodic structure of the multilayer reflective film due to the micro concave and convex surface existing on the substrate It is called a phase defect, and this is a serious problem. It is desirable that there are no concave and convex surfaces having a predetermined size or larger on the substrate. Non-Patent Documents 1 and 2 describe with EUV. The requirements of the cover and the EUV reticle substrate 125722.doc 200830034 are very strict, and the requirements related to their defects are very strict. Non-Patent Document 1 describes the structure of the reflective coating when there are more than 5 〇ηπΐ2 defects on the substrate. Inducing perturbation, resulting in a pattern that protrudes from an unintended shape on the resist layer of the wafer, and does not allow such defects to exist. Non-Patent Document 1 advance description is prominent on the anti-layer of the Si wafer. In terms of the rms (root mean square) roughness of the pattern, the surface roughness of the substrate is required to be less than 〇15 nm to prevent the roughness of the linear edge from increasing. Non-Patent Document 2 describes the main mask coated with the reflective film used in the lithography. A defect of more than 25 nm is not allowed to exist on the surface. Non-Patent Document 3 describes a defect in the extent to which a substrate may be transferred. Non-Patent Document 3 describes that a phase defect may change the line of the printed image. The phase defect of 2 11111 and FWHM (full width at half maximum) of 60 nm surface bump has the following dimensions, whether the size of the phase defect of this size can be transferred and the line width cannot be caused. The boundary condition of the allowable change (the change is 20% of the line width of 35 nm (the line width on the reticle is 14 〇 nm).) In the micro-roughness present on the surface of the substrate, such as foreign matter (particles) or convexity of the fiber Defects can be removed by conventional wet cleaning, brush cleaning, precision polishing, and the like using hydrofluoric acid or aqueous ammonia. However, concave defects such as pits or scratches cannot be removed by their methods. In addition, when applying a wet cleaning material of hydrogen hydride or ammonia, it is necessary to apply a slight coating on the surface of the substrate to remove the convex defects from the substrate by the lift-off system, and the surface of the substrate New concave defects may occur on the substrate. Even when brush cleaning is used to remove the convex defects, new concave defects may be generated on the surface of the substrate. 125722.doc 200830034 Non-Patent Document 1: SEMI, P37-1102 (2002), "Specification for extreme ultraviolet lithography mask substrates*' Non-Patent Document 2: SEMI, P38-1102 (2002), "Specification for absorbing film stacks And multilayers on extreme ultraviolet lithography mask blanks11 Non-Patent Document 3: SPIE, Vol. 4889, Alan Stivers et al., pp. 408-417 (2002), ''Evaluation of the Capability of a

Multibeam Confocal Inspection System for Inspection of EUVL Mask Blanks，、【發明内容】本發明之一目標為提供一種具有凹缺陷（諸如坑或刮痕）之EUV光罩基底用基板表面之平滑方法，以解決先前技術中之上述問題。本發明之另一目標為提供藉由上述基板表面之平滑方法獲得之EUV光罩基底用基板。本發明之另一目標為使用EUV光罩基底用基板提供具有多層反射膜之EUV光罩基底用基板及提供EUV光罩基底。為達成上述目標，本發明提供一種用於EUV微影之反射式光罩基底用基板表面之平滑方法，其包含將含有聚矽氮烷化合物之溶液塗敷至具有凹缺陷之基板表面，且加熱及硬化所塗敷之溶液以形成氧化矽塗層（包含Si02作為主骨幹之塗層），藉此使具有凹缺陷之基板表面平滑（下文稱為 ’’本發明之EUV光罩基底用基板之平滑方法”)。在本發明之EUV光罩基底用基板之平滑方法中，該含有 125722.doc 200830034 聚矽氮烷化合物之溶液較佳具有0.05至2重量％之聚矽氮烷 ·. 化合物濃度。在本發明之EUV光罩基底用基板之平滑方法中，加熱及硬化較佳係在150至500°C之溫度下在含氧氣體環境或含水 1 蒸氣氣體環境下應用。 . 在本發明之EUV光罩基底用基板之平滑方法中，基板表面上之凹缺陷較佳具有30 nm或更小之深度。在本發明之EUV光罩基底用基板之平滑方法中，加熱及 ® 硬化後之凹缺陷較佳具有3 nm或更小之深度。本發明進一步提供用於EUV微影之反射式光罩基底用基板，其具有藉由本發明之EUV光罩基底用基板之平滑方法 (下文稱為’’本發明之EUV光罩基底用基板”）平滑之表面。本發明進一步提供一用於EUV微影之反射式光罩基底之具有多層反射膜之基板，包含本發明之EUV光罩基底用基板。 ^ 本發明進一步提供用於EUV微影之反射式光罩基底，包含本發明之EUV光罩基底用基板。根據本發明之EUV光罩基底用基板之平滑方法，可使具 ’ 有凹缺陷之EUV光罩基底用基板表面平滑，藉此將凹缺陷 - 減小至EUV光罩基底之製造中不具問題之尺寸。凹缺陷減小之程度視凹缺陷之形狀而變化。然而，一種近似法為根據本發明，可使在執行表面拋光及清潔後在EUV光罩基底用基板之膜形成表面上通常存在之具有30 nm或更小深度之凹缺陷之EUV光罩基底用基板表面平滑’且可將凹缺陷 125722.doc 200830034 深度減小至3 nm或更小。基板表面上存在之凸缺陷可藉由使用氣氣酸或氨水之習知濕式清潔法、刷式清潔或精密拋光而移除。然而，當將彼等方法用於移除凸缺陷之目的時，可能會在基板表面上產生新的凹缺陷，但彼等凹缺陷可藉由本發明之Euv光罩基底用基板之平滑方法而減少。此外’當使EUV光罩基底用基板經受諸如拋光之表面加工時’可能會產生作為副產物之凹缺陷。然而，亦可藉由本發明之EUV光罩基底用基板之平滑方法減少該等凹缺此外’在基板表面之凹缺陷成為問題之情況下，當藉由任何方法使基板上之凹缺陷平滑時，重要的為由該膜材料开> 成之平滑表面亦不具有凹缺陷。根據本發明之Ευν光罩基底用基板之平滑方法，平滑表面變為藉由使用由加熱及硬化聚矽氮烷化合物獲得之氧化矽塗層（或包含Si〇2作為主骨幹之塗層）而使表面上不存在引起關於EUV光罩基底製造之問題之尺寸的凹缺陷之情形。認為藉由加熱及硬化聚矽氮烷化合物形成之氧化矽塗層為緊湊且非晶形之氧化矽膜。因此，根據本發明之EUV光罩基底用基板之平滑方法，可提供具有極佳平滑度之EUV光罩基底用基板，其中在膜形成表面上不存在具有引起關於EUV光罩基底製造之問題之尺寸的凹缺陷。【實施方式】 125722.doc 200830034 • 下文描述本發明之EUV光罩基底用基板之平滑方法。 ‘ 本發明之EUV光罩基底用基板之平滑方法用於使EUV光罩基底之基板表面平滑之目的，更特定言之，此基板表面為在EUV光罩基底之製造步驟中形成多層反射膜及吸收層 ^ 之側的基板表面（下文稱為"膜形成表面Ί。可藉由本發明 — 之方法使形成用於靜電吸盤以夾持EUV光罩基底之膜的一側平滑。 Φ 當應用本發明之EUV光罩基底用基板之平滑方法以進行使基板上之凹缺陷平滑之方法時，其包含以諸如氧化鈽、氧化锆或膠態氧化矽之拋光研磨粒子拋光先前提供之EUV 光罩基底用基板之膜形成表面，使用諸如氳氟酸、氫氟矽酸或硫酸之酸性溶液、諸如氨水之鹼性溶液或純水來清潔膜形成表面，且乾燥該清潔表面。當膜形成表面上存在諸如外來物質或纖維之凸缺陷時，則藉由彼等程序移除凸缺陷。鲁較佳將本發明之Euv光罩基底用基板之平滑方法用於在表面拋光及清潔後在模形成表面上存在凹缺陷的基板表面。在表面拋光及清潔I，膜形成表面上不存在極大凹缺陷，且膜形成表面上存在t凹缺陷之深度至多》30nm。需要EUV光罩基底用基板在膜形成表面之整個|面上具有南平坦度及平滑度。特定言之，需要基板之膜形成表面有11]\48(均方根）粗糙度為〇1511瓜或更小且平坦度為 50 nm或更小之平滑表面。即使滿足彼等所要值，膜形成表面上亦可存在稱為坑及刮痕之凹缺陷。 125722.doc 200830034 當膜形成表面上存在之凹缺陷尺寸極小時，該等凹缺陷不會不利影像EUV光罩基底之製造。然而，當膜形成表面上存在特定尺寸或更大尺寸之凹缺陷時，膜形成表面上形成之多層反射膜或吸收層之表面上出現凹缺陷，且可認為該等凹缺陷係EUV光罩基底之缺陷。此外，即使當多層反射膜表面或吸收層表面上未出現凹缺陷時，彼等膜中多層反射結構攝動可形成相缺陷。被認為係EUV光罩基底缺陷之凹缺陷的尺寸視先前不可界定之凹缺陷之形狀而變化。然而作為一種近似法，當基板之膜形成表面上存在深度超過3 nm之凹缺陷時，膜形成表面上形成之多層反射膜或吸收層之表面上可出現凹缺陷’從而導致EUV光罩基底之缺陷。即使當多層反射膜表面或吸收層表面上未出現凹缺陷時，彼等膜中多層反射結構攝動可形成相缺陷。 EUV光罩基底用基板需要極佳的平滑度及平坦度，且除此之外較佳需要低熱膨脹係數（較佳〇士1〇xl〇-8rc，且更佳 0士0.3xl0_V°C)。特定言之，具有低熱膨脹係數之基板之實例包括由具有低熱膨脹係數之玻璃（諸如Si〇2-Ti〇2系統玻璃）製成之基板。然而’基板不限於此，且可使用由已沈澱β-石英固溶體之結晶玻璃製成之基板。 EUV光罩基底用基板較佳對用於在圖案形成後euv光罩基底或遮光罩之清潔及其類似操作的清潔溶劑具有極佳耐久性。此外，EUV光罩基底用基板較佳具有高剛性以防止基板 125722.doc -12- 200830034 上形成之多層反射膜及吸收層之膜應力弓丨起之基板變形。特定言之’具有65 GPa或更高之高揚氏模數（Y〇ung，s modulus)之基板為較佳的。藉由光罩之說明及其類似物適當地夠定EUV光罩基底用基板之尺寸、厚度及其類似物。基板之特定實例包括外形為約6时（152.4 mm)方形且厚度為約〇.25吋（63 mm)之基板。本發明之EUV光罩基底用基板之平滑方法包含將含有聚石夕氮烧化合物之溶液塗敷至基板之具有凹缺陷的媒形成表面上，且加熱及硬化所塗敷之溶液以形成氧化矽塗層（或包含Si〇2作為主骨幹之塗層）’藉此使具有凹缺陷之膜形成表面平滑。 / 本發明可使用以下聚矽氮烷化合物。可使用之聚矽氮烷化合物之實例包括具有由以下通式㈧表示之結構單元a及由以下通式(b)表示之工有機聚矽氮烷化合物。的 R1Multibeam Confocal Inspection System for Inspection of EUVL Mask Blanks, SUMMARY OF THE INVENTION An object of the present invention is to provide a smoothing method for a substrate surface of an EUV reticle substrate having concave defects such as pits or scratches to solve the prior art. The above problems in the middle. Another object of the present invention is to provide a substrate for an EUV mask substrate obtained by the smoothing method of the above substrate surface. Another object of the present invention is to provide a substrate for an EUV reticle substrate having a multilayer reflective film using an EUV reticle substrate and to provide an EUV reticle substrate. In order to achieve the above object, the present invention provides a smoothing method for a surface of a substrate for a reflective reticle substrate for EUV lithography, which comprises applying a solution containing a polyazide compound to a surface of a substrate having a concave defect, and heating And hardening the applied solution to form a yttria coating (including a coating of SiO 2 as a main backbone), thereby smoothing the surface of the substrate having the concave defect (hereinafter referred to as 'the substrate for the EUV reticle substrate of the present invention The smoothing method"). In the smoothing method of the substrate for an EUV mask substrate of the present invention, the solution containing the 125722.doc 200830034 polyazane compound preferably has a polyazoxide of 0.05 to 2% by weight. In the smoothing method of the substrate for an EUV reticle substrate of the present invention, heating and hardening are preferably applied at an atmosphere of 150 to 500 ° C in an oxygen-containing gas atmosphere or an aqueous 1 vapor gas atmosphere. In the smoothing method of the substrate for the EUV reticle substrate, the concave defect on the surface of the substrate preferably has a depth of 30 nm or less. In the smoothing method of the substrate for the EUV reticle substrate of the present invention, heating And the cured concave defect preferably has a depth of 3 nm or less. The present invention further provides a substrate for a reflective reticle substrate for EUV lithography, which has smoothness of the substrate for the EUV reticle substrate of the present invention. The method (hereinafter referred to as 'the substrate for EUV reticle substrate of the present invention') has a smooth surface. The present invention further provides a substrate having a multilayer reflective film for a reflective reticle substrate for EUV lithography, comprising the substrate for an EUV reticle substrate of the present invention. The present invention further provides a reflective reticle substrate for EUV lithography comprising the substrate for an EUV reticle substrate of the present invention. According to the smoothing method of the substrate for an EUV reticle substrate according to the present invention, the surface of the substrate for the EUV reticle substrate having a concave defect can be smoothed, thereby reducing the concave defect to the manufacturing of the EUV reticle substrate without problems. size. The degree of reduction of the concave defect varies depending on the shape of the concave defect. However, an approximation is according to the present invention, and it is possible to use an EUV mask substrate having a concave defect of 30 nm or less which is usually present on the film formation surface of the substrate for an EUV reticle substrate after surface polishing and cleaning. The substrate surface is smooth 'and the depth of the concave defect 125722.doc 200830034 can be reduced to 3 nm or less. The convex defects existing on the surface of the substrate can be removed by a conventional wet cleaning method, brush cleaning or precision polishing using a gas acid or ammonia water. However, when these methods are used for the purpose of removing convex defects, new concave defects may be generated on the surface of the substrate, but the concave defects may be reduced by the smoothing method of the substrate for the Euv mask substrate of the present invention. . Further, when the substrate for an EUV reticle substrate is subjected to surface processing such as polishing, a concave defect as a by-product may be generated. However, it is also possible to reduce the recesses by the smoothing method of the substrate for the EUV mask substrate of the present invention. Further, when the concave defects on the surface of the substrate become a problem, when the concave defects on the substrate are smoothed by any method, It is important that the smooth surface formed by the film material does not have concave defects. According to the smoothing method of the substrate for the 光ν mask substrate according to the present invention, the smooth surface is changed by using a ruthenium oxide coating obtained by heating and hardening the polyazane compound (or a coating containing Si〇2 as a main backbone) There is no such thing as a concave defect on the surface that causes the size of the problem with the manufacture of the EUV mask substrate. It is considered that the ruthenium oxide coating formed by heating and hardening the polyazane compound is a compact and amorphous ruthenium oxide film. Therefore, according to the smoothing method of the substrate for an EUV reticle substrate of the present invention, it is possible to provide a substrate for an EUV reticle substrate having excellent smoothness, in which there is no problem on the film forming surface which causes problems concerning the manufacture of the EUV reticle substrate. Concave defects in size. [Embodiment] 125722.doc 200830034 • A method of smoothing the substrate for an EUV mask substrate of the present invention is described below. The smoothing method of the substrate for an EUV reticle substrate of the present invention is for the purpose of smoothing the surface of the substrate of the EUV reticle substrate, more specifically, the surface of the substrate is a multilayer reflective film formed in the manufacturing step of the EUV reticle substrate and The surface of the substrate on the side of the absorbing layer (hereinafter referred to as "film forming surface Ί. The side of the film for forming the electrostatic chuck to hold the EUV reticle substrate can be smoothed by the method of the present invention. Φ When applying the present The method for smoothing a substrate for an EUV reticle substrate of the invention for performing a method of smoothing concave defects on a substrate, comprising polishing a previously provided EUV reticle substrate with polishing abrasive particles such as yttria, zirconia or colloidal cerium oxide Forming a surface with a film of a substrate, using an acidic solution such as hydrofluoric acid, hydrofluoric acid or sulfuric acid, an alkaline solution such as aqueous ammonia or pure water to clean the film forming surface, and drying the cleaning surface. When present on the film forming surface When a convex defect such as a foreign matter or a fiber is used, the convex defect is removed by the procedure. Lu preferably uses the smoothing method of the substrate for the Euv mask substrate of the present invention. After surface polishing and cleaning, there is a concave defect on the surface of the substrate. On the surface polishing and cleaning I, there is no large concave defect on the surface of the film formation, and the depth of the concave defect on the surface of the film formation is at most 30 nm. The EUV reticle substrate has a south flatness and smoothness on the entire surface of the film forming surface. In particular, it is required that the film forming surface of the substrate has an 11]\48 (root mean square) roughness of 〇1511 melon or A smooth surface having a smaller flatness of 50 nm or less. Even if the desired values are satisfied, there may be concave defects called pits and scratches on the film forming surface. 125722.doc 200830034 When the film is formed on the surface When the size of the concave defect is extremely small, the concave defects do not adversely affect the fabrication of the image EUV reticle substrate. However, when a concave defect of a specific size or larger is present on the film forming surface, the film is formed on the surface of the multilayer reflective film or Concave defects appear on the surface of the absorbing layer, and the concave defects are considered to be defects of the EUV reticle base. Further, even when the surface of the multilayer reflective film or the surface of the absorbing layer does not have concave defects The perturbation of the multilayer reflective structure in the films can form phase defects. The size of the concave defect considered to be the defect of the EUV mask base varies depending on the shape of the previously undefined concave defect. However, as an approximation, when the film of the substrate When a concave defect having a depth of more than 3 nm is formed on the surface, a concave defect may occur on the surface of the multilayer reflective film or the absorbing layer formed on the film forming surface to cause defects of the EUV reticle substrate even when the surface of the multilayer reflective film or absorption When no concave defects appear on the surface of the layer, the multi-layer reflective structure perturbation in these films can form phase defects. The substrate for the EUV mask substrate needs excellent smoothness and flatness, and in addition, a low thermal expansion coefficient is preferably required. (Better gentleman 1〇xl〇-8rc, and better 0±0.3xl0_V°C). Specifically, examples of the substrate having a low coefficient of thermal expansion include a substrate made of a glass having a low coefficient of thermal expansion such as Si〇2-Ti〇2 system glass. However, the substrate is not limited thereto, and a substrate made of crystallized glass having precipitated β-quartz solid solution can be used. The EUV reticle substrate preferably has excellent durability against cleaning solvents for cleaning of the euv reticle substrate or hood after pattern formation and the like. Further, the substrate for the EUV reticle base preferably has high rigidity to prevent deformation of the substrate which is formed by the multilayer reflection film formed on the substrate 125722.doc -12-200830034 and the film stress of the absorbing layer. A substrate having a high Young's modulus of 65 GPa or more is preferred. The size, thickness, and the like of the EUV reticle substrate are appropriately determined by the description of the reticle and the like. Specific examples of the substrate include a substrate having a square shape of about 6 o'clock (152.4 mm) and a thickness of about 吋25 吋 (63 mm). The method for smoothing a substrate for an EUV reticle substrate of the present invention comprises applying a solution containing a polysulfide compound to a surface of a substrate having a concave defect, and heating and hardening the applied solution to form cerium oxide. The coating (or a coating comprising Si〇2 as the main backbone) is used to smooth the surface of the film having concave defects. / The following polyazide compounds can be used in the present invention. Examples of the polyazane compound which can be used include a structural unit a represented by the following general formula (VIII) and an organopolyazane compound represented by the following general formula (b). R1

I —Si —(NH) —I —Si —(NH) —

I R2 (A) R3I R2 (A) R3

I —Si — 〇 —I —Si — 〇 —

I R4 (B) 125722.doc -13- 200830034 在上述有機聚矽氮烷化合物中，結構單元（A)及（B)各自通苇为別表示為Am & Bn形式，其中瓜及立為正整數。此亦適用於下文所述之結構單元（(：）至（1)。在上述通式（A)及（B)中，R1、R2、R3&R4表示選自由烷基、烯基、環烷基、芳基、芳烷基、烷基胺基、烷基矽烷基及烷氧基組成之群之基團或氫，其限制條件為…及以不同時為氫，且R3及R4不同時為氫。有機聚矽氮烷化合物可進一步具有由以下通式（c)表示之結構單元C。 R5 R8 I I —Si —R7 —Si —I R4 (B) 125722.doc -13- 200830034 In the above organopolyazane compound, each of the structural units (A) and (B) is expressed as an Am & Bn form, wherein the melon is positive Integer. This also applies to the structural units ((:) to (1) described below. In the above formulae (A) and (B), R1, R2, R3& R4 are selected from an alkyl group, an alkenyl group, and a cycloalkane. a group of a group consisting of a group consisting of a aryl group, an aryl group, an arylalkyl group, an alkylamino group, an alkylalkyl group, and an alkoxy group, or hydrogen, the limiting conditions being ... and not simultaneously hydrogen, and R3 and R4 are not simultaneously Hydrogen. The organopolyazane compound may further have a structural unit C represented by the following formula (c): R5 R8 II — Si — R 7 — Si —

上述有機聚矽氮烷化合物可進一 ’ R5、R6、R8及R9各自表示選自由由、芳基、芳烷基、烷基胺基、烷基矽二群之基團或氫，其限制條件為R5、氫。R7表示二價芳族基。式（D)表示之結構單元D、經以The above organopolyazane compound may be further represented by a group selected from the group consisting of an aryl group, an aryl group, an arylalkyl group, an alkylamino group, an alkyl group, or a hydrogen group. R5, hydrogen. R7 represents a divalent aromatic group. Structural unit D represented by formula (D)

構單元。一步具有選自由經以下通〇、經以下通式（E)表示之結構單元E 之結構單元F組成之群的至少一個結 125722.doc -14· 200830034 R10Construction unit. One step has at least one junction selected from the group consisting of structural units F of the structural unit E represented by the following general formula (E) 125722.doc -14· 200830034 R10

I —Si —(NH) —I —Si —(NH) —

I (D)I (D)

H R11H R11

I -Si-(NH) r5 (E) R12I -Si-(NH) r5 (E) R12

I R14-Si-(NH)05-I R14-Si-(NH)05-

I 13 (F) 在上述通式（D)、（E)及（F)中，r1。、R11、R12、R13 及 R14 各自表示選自由烷基、烯基、環烷基、芳基、芳烷基、烷基胺基、烷基矽烷基及烷氧基組成之群之基團。I 13 (F) In the above formulae (D), (E) and (F), r1. And R11, R12, R13 and R14 each represent a group selected from the group consisting of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group, an alkylalkyl group and an alkoxy group.

上述有機聚矽氮烷化合物可進一步具有選自由經以下通卷（G)表示之結構單元g、經以下通式（H)表示之結構單元η 及經以下通式（I)表示之結構單元〗組成之群的 R15The above organopolyazide compound may further have a structural unit η selected from the following structural formula (G), a structural unit η represented by the following general formula (H), and a structural unit represented by the following general formula (I) Group of R15

I —Si —(NH) —R16—(ΝΗ) —I —Si —(NH) —R16—(ΝΗ) —

I Η (G) 125722.doc -15- 200830034 R17I Η (G) 125722.doc -15- 200830034 R17

I —S i — (NH) — R19 — (NH)—I —S i — (NH) — R19 — (NH)—

I (H) (I) R18 R20I (H) (I) R18 R20

I — Si — ((NH) — R21 — (NH)) L5— 在上述通式（G)、（H)及（I)中，R15、R17、尺以及R2〇各自表示選自由烷基、烯基、環烷基、芳基、芳烷基、烷基胺基、烷基矽烷基及烷氧基組成之群之基團，且、R!9及 R21各自表示二價芳族基。在上述通式（A)至⑴中，較佳地，烷基為C1至C3烷基，烯基為C1至C2烯基，環烷基為C6至C8環烷基，芳基為C6 至C8芳基，芳烷基為C1至C3芳烷基，烷基胺基為C1至C3 烷基胺基，烷基矽烷基為C1至C3烷基矽烷基，且烷氧基為C1至C3烷氧基。在上述通式（C)、（G)、（H)及⑴中，二價芳族基較佳為伸芳烧基（aralkylene group)或伸芳基，且尤其較佳為伸苯基、伸甲苯基、二甲苯基（Xylylene gr〇Up)、苯亞曱基、亞本乙基、α-甲基苯亞甲基、苯亞烯丙基（cinnaniyiidene group)或伸萘基。二價芳族基R7、R16、R19及R21之其他較佳實施例包括由以下通式表示之基團。 125722.doc •16- 200830034 z 一I — Si — ((NH) — R21 — (NH)) L5—In the above formulae (G), (H) and (I), R15, R17, ruthenium and R2〇 each represent an alkyl group or an ene group. a group consisting of a group consisting of a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group, an alkylalkyl group, and an alkoxy group, and each of R!9 and R21 represents a divalent aromatic group. In the above formulae (A) to (1), preferably, the alkyl group is a C1 to C3 alkyl group, the alkenyl group is a C1 to C2 alkenyl group, the cycloalkyl group is a C6 to C8 cycloalkyl group, and the aryl group is a C6 to C8 group. Aryl, aralkyl is C1 to C3 aralkyl, alkylamino is C1 to C3 alkylamino, alkyl fluorenyl is C1 to C3 alkyl decyl, and alkoxy is C1 to C3 alkoxy base. In the above formulae (C), (G), (H) and (1), the divalent aromatic group is preferably an aralkylene group or an aryl group, and particularly preferably a phenyl group or a stretching group. Tolyl, xylylene gr〇Up, benzylidene, subunit ethyl, α-methylbenzylidene, cinnaniyiidene group or naphthyl. Other preferred embodiments of the divalent aromatic group R7, R16, R19 and R21 include a group represented by the following formula. 125722.doc •16- 200830034 z One

(R22) a 上述通式中之R22表示鹵素原子或低碳烷基，且較佳為 C1至C3烷基。 a為0至4之整數，且z為直接鍵結的或表示由以下通式表示之基團。(R22) a R22 in the above formula represents a halogen atom or a lower alkyl group, and is preferably a C1 to C3 alkyl group. a is an integer from 0 to 4, and z is directly bonded or represents a group represented by the following general formula.

上述通式中之R23表示鹵素原子或低碳烷基，且較佳為 C1至C3烷基，13為0至4之整數^ 丫為直接鍵結的或表示二價鍵。較佳地，Y為直接鍵結的，或為_〇_、_s_、{仏-或一 CH2CH2-。 ^R23 in the above formula represents a halogen atom or a lower alkyl group, and preferably a C1 to C3 alkyl group, and 13 is an integer of 0 to 4, which is directly bonded or represents a divalent bond. Preferably, Y is directly bonded, or is _〇_, _s_, {仏- or a CH2CH2-. ^

—一1貝方務基R，、各自尤其較佳為選自由伸苯f、伸甲苯基、二甲苯基、苯亞甲基、亞苯乙基、心甲基苯亞f基、苯亞烯丙基及伸萘基組成之群的基團。在上述有機聚石夕氮烧化合物中，當SM)鍵數㈣心且⑴ 尤其較佳為 0.80 至〇.95。tw(NsiN+Nsi·。）小於〇， ^性模數趨向於增加’且化合物變得脆性。當其超過〇.99 0，，有機聚梦氮燒中之交聯點減少，且硬度變得不足。 125722.doc -17- 200830034 可藉由例如 JP_A-2005_36089 及 JP-A-2004-77874 中所述之習知方法合成有機聚矽氮烷化合物。舉例而言，在置於恆溫室中之反應容器内置放乾氮氣，且將藉由將47 g(0.222莫耳）苯基三氯矽烷（PhSiCl3)、56 g (0.222 莫耳）二苯基二氯矽烷（ph2Sicl2)、3·8 g(〇〇33莫耳）甲基二氯矽烷（MeSiHCh)及50 g(0.19莫耳）1，4·雙（二甲基氯石夕烧基）苯溶解於15〇00 ml二曱苯中獲得之混合物引入反應容器中。將反應容器内之溫度設定為_5。〇，且將藉由將丨3 〇 g (0.7222莫耳）水溶解於1〇〇〇 ml吡啶中而獲得之溶液以約3〇 ml/min之速率倒入反應容器中。此時，在傾倒同時發生鹵石夕烧與水之間的反應，且容器内之溫度升至_2〇c。水與吡淀之混合溶液傾倒完成後，持續攪拌1小時。此後，以2莫耳/min之速率傾倒氨氣歷時1〇分鐘，以達使未反應之氯矽烧完全反應之目的，接著攪拌。反應完成後，向容器中吹入乾氮氣以移除未反應之氨氣，且將反應混合物在氮氣氣體環〗兄壓力下過渡以獲得約2,300 ml濾液。當在減壓下將濾液/谷劑替換後，獲得丨〇〇 g呈無色、透明且黏性樹脂之有機聚石夕氮燒化合物a 1。所獲得有機聚矽氮烷化合物之數量平均分子量為 2,200，且其為具有結構單元A(其中r1&r2為苯基）、結構單元B (其中R及R4為苯基）、結構單元C (其中r5、r6、r8 及R為CH3，且R7為苯基）、結構單元D(其中化10為CH3)及結構單元E(其中Ru為苯基）之有機聚矽氮烷化合物。 125722.doc -18- 200830034 . 當使有機聚矽氮烷化合物al經受IR光譜分析時，確認基於N-H基團之吸收在波長3,350 cm-1處，基於Si-H之吸收在 2，160 cm·1處，基於Si-Ph基團之吸收在1，140 cnT1處，基於 Si-O之吸收在1，〇6〇至i，i〇〇 cm·1處，基於si-H及Si-N-Si之 ^ 吸收在I020至820 cm·1處，基於C_H之吸收在3，140 cm·1、 • 2,980 cm·1及l^OcnT1處，且基於苯環之OH的吸收在810 crrT1 及 780 cnT1 處。鲁當量測有機聚矽氮烷化合物al之1H-NMR光譜時，確認 δ7·2 ppm (br，C6H5)、δ4·8 ppm (br，SiH)、δΐ.4 ppm (br， NH)及 δ0·3 ppm (br，SiCH3)之吸收。有機聚矽氮烷化合物al2Nsi 〇/(Nsi N+Nsi 〇)之理論值為 0.928 〇可使用之有機聚矽氮烷化合物之其他實例包括JP-A_ 2005-36089及心_2_而4中所揭示之有機聚石夕氮烧化合物。 • 具有由以下通式⑴表示之結構單元ί之無機聚碎氮貌化合物亦可用作聚矽氮烷化合物。- a 1 Å square base R, each particularly preferably selected from the group consisting of phenylene, tolyl, xylyl, benzylidene, phenylene, phenylmethyl phenyl, phenylallyl And a group consisting of a group consisting of naphthyl groups. In the above organic polysulfide compound, when SM) is a bond number (four) and (1) is particularly preferably from 0.80 to 〇.95. Tw (NsiN + Nsi·.) is less than 〇 , the ^ modulus tends to increase 'and the compound becomes brittle. When it exceeds 〇.99 0, the cross-linking point in the organic polynitrogen blast is reduced, and the hardness becomes insufficient. The organopolyazane compound can be synthesized by a conventional method as described in JP-A-2005-36089 and JP-A-2004-77874, for example. For example, the reaction vessel placed in the thermostatic chamber is internally filled with dry nitrogen and will be charged with 47 g (0.222 mol) of phenyltrichloromethane (PhSiCl3), 56 g (0.222 mol) of diphenyl Chlorodecane (ph2Sicl2), 3·8 g (〇〇33 mol) methyldichlorodecane (MeSiHCh) and 50 g (0.19 mol) 1,4·bis (dimethylchlorosulphate) benzene dissolved A mixture obtained in 15 〇 ml of diphenylbenzene was introduced into the reaction vessel. The temperature in the reaction vessel was set to _5. 〇, and the solution obtained by dissolving 丨3 〇 g (0.7222 mol) of water in 1 〇〇〇 ml of pyridine was poured into the reaction vessel at a rate of about 3 〇 ml/min. At this time, the reaction between the brine and the water occurred at the same time as the pouring, and the temperature inside the vessel rose to _2 〇 c. After the mixture of water and pyrolysis was poured, stirring was continued for 1 hour. Thereafter, the ammonia gas was poured at a rate of 2 mol/min for 1 Torr for the purpose of completely reacting the unreacted chloranil, followed by stirring. After completion of the reaction, dry nitrogen gas was blown into the vessel to remove unreacted ammonia gas, and the reaction mixture was transiently pressurized under a nitrogen gas loop to obtain about 2,300 ml of filtrate. When the filtrate/trolus was replaced under reduced pressure, an organic polysulfide compound a 1 having a colorless, transparent and viscous resin was obtained. The obtained organopolyazane compound has a number average molecular weight of 2,200, and it has a structural unit A (wherein r1 & r2 is a phenyl group), a structural unit B (wherein R and R4 are a phenyl group), and a structural unit C (wherein An organopolyazane compound in which r5, r6, r8 and R are CH3 and R7 is a phenyl group, a structural unit D (wherein 10 is CH3) and a structural unit E (wherein Ru is a phenyl group). 125722.doc -18- 200830034. When the organopolyazide compound al was subjected to IR spectroscopy, it was confirmed that the absorption based on the NH group was at a wavelength of 3,350 cm-1, and the absorption based on Si-H was 2,160 cm· At 1 position, the absorption based on Si-Ph group is at 1,140 cnT1, and the absorption based on Si-O is at 1, 〇6〇 to i, i〇〇cm·1, based on si-H and Si-N- The absorption of Si is at I020 to 820 cm·1, based on C_H absorption at 3,140 cm·1, • 2,980 cm·1 and l^OcnT1, and the absorption of OH based on benzene ring is at 810 crrT1 and 780 cnT1 At the office. When the 1H-NMR spectrum of the organopolyazane compound a was measured, it was confirmed that δ7·2 ppm (br, C6H5), δ4·8 ppm (br, SiH), δΐ.4 ppm (br, NH) and δ0 · Absorption of 3 ppm (br, SiCH3). The theoretical value of the organopolyazane compound al2Nsi 〇/(Nsi N+Nsi 〇) is 0.928 其他 Other examples of organopolyazane compounds which can be used include JP-A_2005-36089 and heart _2_4 An organic polysulfide compound is disclosed. • An inorganic polynitramine compound having a structural unit represented by the following general formula (1) can also be used as a polyazane compound.

Η I —Si — (NH)— Η (J) 在上述無機聚矽氮燒合-浓4甘a, 卿T結構早兀了一般表示為& 开/式’其中1為正整數。j一船至200。奴為10至10,0〇〇，且通常為10 125722.doc • 19- 200830034 在上述結構單元J中，其端基未受特定限制，但一般為矽烷基'甲基、胺基、甲氧基、烷氧基或三甲基矽烷基。此外’為與諸如有機聚矽氮烷化合物之其他組份鍵結，結構單元j可具有羧基、胺基、羥基、羰基或其類似基團作為端基。具有結構單元j之無機聚矽氮烷化合物之特定實例包括全氫I砍氮燒。全氫聚矽氮烷之製造方法描述於（例如）Jp_ A-60-145903 及 D. Seyferth #、iC〇mmUnicati〇nofAm·Η I —Si — (NH)—Η (J) In the above-mentioned inorganic polyfluorene-sintering-concentration 4 Gan, the structure of the T is as long as it is generally expressed as & open / where '1 is a positive integer. j a boat to 200. The slave is 10 to 10,0 〇〇, and usually 10 125722.doc • 19- 200830034 In the above structural unit J, the terminal group thereof is not particularly limited, but is generally a decyl group 'methyl group, an amine group, a methoxy group. Alkyl, alkoxy or trimethyldecyl. Further, in order to bond with other components such as an organopolyazane compound, the structural unit j may have a carboxyl group, an amine group, a hydroxyl group, a carbonyl group or the like as a terminal group. Specific examples of the inorganic polyazirane compound having the structural unit j include perhydrogen iodine. A method for producing perhydropolyazane is described, for example, in Jp_A-60-145903 and D. Seyferth #, iC〇mmUnicati〇nofAm·

Cer. Sor·，c-13, 1 月（1982)中。舉例而言’將氣體吹管、機械攪拌器及杜而（Dewar)冷 /旋裔裝配至内部體積為1公升之四頸燒瓶，且將反應容器内部替換為脫氧乾氮氣。將490 ml無水吡啶引入至四頸燒瓶中，且將該燒瓶冰冷卻。將5 1.9 g二氯石夕烧添加至燒瓶中以形成白色固體加合物 (SiH2Cl2_2C2H5N)。將反應混合物冰冷卻，且在擾拌反應混合物下將51.0 g氨氣吹入燒瓶中，該氨氣係經穿過氫氧化鈉管（吸附管）及活性碳而純化。接著將反應混合物加熱至 100〇C 〇反應完成後’將反應混合物離心，且使用無水σ比咬洗滌。將反應混合物在乾燥氮氣氣體環境下過據獲得85〇 ml 濾、液。自5 mH慮液移除溶劑以獲得〇· 1 〇2 g樹脂性固體全氫聚石夕氮烧。當以GPC量測時，所獲得之全氫聚矽氮烷具有ι，1〇〇之數量平均分子量（計算為聚苯乙烯）。 125722.doc -20 - 200830034 當進打IR光譜分析時，確認基於n_h之吸收在波長3,39〇及1’18〇處，基於Si-H之吸收在2，170 cnT1處且基於Si_N_Si之吸收在至咖處。Cer. Sor·, c-13, January (1982). For example, a gas blower, a mechanical stirrer, and a Dewar cold/ring were assembled to a four-necked flask having an internal volume of 1 liter, and the inside of the reaction vessel was replaced with deoxygenated dry nitrogen. 490 ml of anhydrous pyridine was introduced into a four-necked flask, and the flask was ice-cooled. 51.9 g of dichlorite was added to the flask to form a white solid adduct (SiH2Cl2_2C2H5N). The reaction mixture was ice-cooled, and 51.0 g of ammonia gas was blown into the flask under a scrambled reaction mixture, which was purified by passing through a sodium hydroxide tube (adsorption tube) and activated carbon. The reaction mixture was then heated to 100 ° C. After the reaction was completed, the reaction mixture was centrifuged and washed with anhydrous σ. The reaction mixture was passed through a dry nitrogen atmosphere to obtain 85 mL of a filtrate. The solvent was removed from the 5 mH solution to obtain 〇·1 〇 2 g of a resinous solid perhydropolylite. When measured by GPC, the obtained perhydropolyazane had an average molecular weight of ι, 1 ( (calculated as polystyrene). 125722.doc -20 - 200830034 When entering the IR spectrum analysis, confirm that the absorption based on n_h is at the wavelengths of 3, 39〇 and 1'18〇, based on the absorption of Si-H at 2,170 cnT1 and based on the absorption of Si_N_Si In the coffee shop.

具有上述結構單元八至！之有機聚石夕氮烧化合物及具有結構單7L J之無機聚發氮烷化合物可組合使用。在此狀況下彼等化合物之摻合比例可視情況根據目的而選擇，但無機聚石夕乳烧化合物之摻合比例較佳為每1〇〇質量份有機聚石夕氮烧化合物及無機聚石夕氮烧化合物之總和的9〇質量份或更少，且更佳為50質量份或更少。田摻口比例改變時’藉由塗敷含有聚石夕氣烧化合物之溶液且m a塗敷之溶液所獲得之膜硬度改變。因此，較佳根據需要適當地選擇彼等化合物之摻合比例。本^明所用之聚石夕氮燒化合物較佳具有約5〇〇至⑽之數量平均分子量。藉由使聚石夕氮燒化合物與具有經基之物質反應而使其水解。為此’水或醇類溶劑不可用作聚⑨氮烧化合物之溶劑。此外，酮型溶劑及醚型溶劑溶解於水，且較不佳。出於溶解度、穩定性及塗層特性之目的，聚錢烧化合物之溶劑較佳為高沸點芳族溶劑及礦物辖類，且可為諸如二丁基醚之醚型溶劑。在本發明中，塗敷至爾光罩基底用基板之膜形成表面的♦液之聚矽氮烷化合物濃度較佳為〇〇5至2重量％。聚矽氮烷化合物之濃度小於0.05重量％時，藉由塗敷含有聚矽氮燒化合物之溶液，隨後加熱且硬化所形成之氧切塗層 125722.doc •21, 200830034 (或包含Si〇2作為主骨幹之塗層）之膜厚度過薄，且因此平滑具有凹缺陷之膜形成表面的效應變得不足。當聚矽氮烷化合物濃度超過2重量％，藉由塗敷含有聚矽氮烷化合物之溶液’隨後加熱且硬化形成之氡化矽塗層（或包含Si〇2 作為主骨幹之塗層）厚度之均一性劣化，導致EUV光罩基底用基板特性（諸如基板之平坦度及表面粗糙度）劣化。此外，儘管視所用之塗佈方法而定，含有聚矽氮烷化合物之溶液的塗層特性劣化。Have the above structural unit eight to! The organic polysulfide compound and the inorganic polyrotaxane compound having the structure of 7L J can be used in combination. In this case, the blending ratio of the compounds may be selected according to the purpose, but the blending ratio of the inorganic polysorbent compound is preferably 1 part by mass of the organic polysulfide compound and the inorganic poly stone. 9 parts by mass or less, and more preferably 50 parts by mass or less, based on the total of the nitrogen-sintering compounds. When the ratio of the field doping is changed, the film hardness obtained by coating the solution containing the polysulfide compound and the solution coated with m a changes. Therefore, it is preferred to appropriately select the blending ratio of the compounds as needed. The polysulfide compound used in the present invention preferably has a number average molecular weight of from about 5 Å to (10). The polysulfide compound is hydrolyzed by reacting it with a substance having a radical. For this reason, water or an alcohol solvent is not used as a solvent for the poly 9 nitrogen compound. Further, the ketone type solvent and the ether type solvent are dissolved in water and are less preferred. For the purpose of solubility, stability and coating properties, the solvent of the polyglycol compound is preferably a high-boiling aromatic solvent and minerals, and may be an ether-type solvent such as dibutyl ether. In the present invention, the concentration of the liquid polyazinane compound applied to the film forming surface of the substrate for the reticle base substrate is preferably 〇〇5 to 2% by weight. When the concentration of the polyazide compound is less than 0.05% by weight, the oxygen-cut coating formed by coating the solution containing the polyazide-sintering compound, followed by heating and hardening is 125722.doc • 21, 200830034 (or contains Si〇2) The film thickness as the coating of the main backbone is too thin, and thus the effect of smoothing the film forming surface having the concave defect becomes insufficient. When the concentration of the polyazide compound exceeds 2% by weight, the thickness of the bismuth telluride coating (or the coating containing Si〇2 as the main backbone) formed by coating a solution containing the polyazide compound followed by heating and hardening The uniformity of the deterioration deteriorates the substrate characteristics (such as the flatness and surface roughness of the substrate) of the EUV mask substrate. Further, although the coating property of the solution containing the polyazide compound is deteriorated depending on the coating method used.

塗敷至EUV光罩基底用基板之膜形成表面之溶液除聚矽氮烷化合物及溶劑外可視需要含有其他組份。可含於溶劑中之其他組份之實例包括作為聚矽氮烷化合物至氧化矽之轉化反應的促進劑之催化劑及聚合引發劑。該等催化劑之特定實例包括作為無機催化劑之pd化合物。此外，有機催化劑之實例包括胺型催化劑。當塗敷彼等催化劑時，認為在更低溫下硬化（例如在室溫下硬化）為可能的。另一實例包括UV引發劑，添咖該引發劑以藉由紫外線（uv)韓射進二聚石夕氮燒化合物至氧切之轉化反應。tguv輕射時’認為在室溫下硬化為可能的。含有聚矽氮烷化合物之溶液可選自市售產品。該等市隹 ^之實例包括 ALCEDAR C0AT，Cladant 如叫巧稭由習知 m有聚矽氮烷化合物之溶液的塗法4方法諸如旋塗法、浸潰法、滾塗法、棒塗法、嗔塗法、刷塗法及其類似方法。其中，出於可將溶液均一地 125722.doc -22- 200830034 ί::::成表面之㈣’旋塗法或浸潰法為較佳的，且 2疋_ :較佳。當選擇旋塗法時’旋轉速度較佳為，rpm或更尚rpm以獲得均一之膜形成。The solution applied to the film forming surface of the substrate for the EUV mask base may optionally contain other components in addition to the polyazane compound and the solvent. Examples of the other components which may be contained in the solvent include a catalyst which is a promoter of a conversion reaction of a polyazide alkane compound to cerium oxide, and a polymerization initiator. Specific examples of such catalysts include pd compounds as inorganic catalysts. Further, examples of the organic catalyst include an amine type catalyst. When applying these catalysts, it is considered that it is possible to harden at a lower temperature (for example, hardening at room temperature). Another example includes a UV initiator which is added to the conversion reaction of the dimeric sulphide compound to oxygen scavenging by ultraviolet (uv) han. When tguv is lightly shot, it is considered that hardening at room temperature is possible. The solution containing the polyaziridine compound may be selected from commercially available products. Examples of such municipalities include ALCEDAR C0AT, which is a coating method of a solution of a polyoxazane compound, such as a spin coating method, a dipping method, a roll coating method, a bar coating method, or the like. Dipping method, brushing method and the like. Among them, a (four)' spin coating method or a dipping method in which the solution is uniformly 125722.doc -22-200830034 ί:::: is preferable, and 2 疋 _ : is preferable. When the spin coating method is selected, the 'rotation speed is preferably rpm or rpm to obtain a uniform film formation.

塗敷含有聚錢烧化合物之溶液後，將基板在含氧氣體環境或含水蒸氣氣體環境巾加熱且硬化。結果，聚錢烧化合=與氧或水蒸氣在氣體環境下反應，且轉化為氧化矽，猎此在基板之膜形成表面上形成氧化矽塗層(或包含 SW2作為主骨幹之塗層）。本文所用之含氧氣體環境意謂氣體環境中存在氧，且氣體環境中氧濃度不受特定限制。本文所用t含水蒸氣氣體環境意謂氣體環境中存在水蒸氣，且氣體環境中水蒸氣濃度不受特定限制。目此，可= 工氣中執yf亍加熱及硬化。加熱及硬化溫度視所用聚矽氮烷化合物種類及溶液中聚矽氮烷化合物濃度而變化，但加熱及硬化較佳係在MO至 5〇〇°C之溫度下進行。當加熱及硬化溫度低於^❹它時，聚矽氮烷化合物至氧化矽之轉化進行的不充分，且因此不能形成具有足夠厚度以平滑凹缺陷之氧化矽塗層（或包含 Si〇2作為主骨幹之塗層）。當加熱及硬化溫度超過5〇(rc 時，烘培（加熱及硬化）溫度高於基板之應變點（儘管視基板材料而定），且因此基板可能變形。加熱及硬化溫度更佳為150至400°C。當如前文所述使用諸如催化劑或聚合引發劑之轉化反應促進劑時，認為在顯著低溫下硬化（例如在室溫下硬化）為可能的。此外，當施加UV輻射時，認為在室溫下硬化為 125722.doc -23- 200830034 . 可能的。 - 在本發明中，具有凹缺陷之膜形成表面係藉由在Euv光罩基底用基板之具有凹缺陷的膜形成表面上形成氧化石夕塗層（或包含si〇2作為主骨幹之塗層），尤其認為係緊凑且非 ^形氧切塗層的塗層而得以平滑。形成塗層後之膜形成 . 表面意謂氧化矽塗層（或包含Si〇2作為主骨幹之塗層）的表面。在平滑具有凹缺陷之膜形成表面之狀況了，膜㈢形絲 Φ 面（亦即塗層表面）不必成為根本不存在凹缺陷之情形，且若僅將塗層表面上存在之凹缺陷平滑至使得對Euv光罩基底用基板不產生問題之尺寸即為足夠的。作為EUV光罩基底之缺陷的凹缺陷之尺寸視凹缺陷之形狀而變化，且不能經完全定義。作為一種近似法，當基板之膜形成表面上存在深度超過3 nm之凹缺陷時，膜形成表面上形成之多層反射膜或吸收層之表面上可出現凹缺陷，且遺荨缺陷可成為EUV光罩基底之缺陷。即使當多層反射 φ 膜或吸收層之表面上未出現凹缺陷時，彼等膜中結構攝動可引起相缺陷。為此，塗層表面上存在之凹缺陷之深度較佳為3 nm或更低，且更佳為1 nm或更低。塗層表面相較於EUV光罩基底用基板之膜形成表面可具，有不良表面粗糙度，儘管視所形成塗層之組份、膜厚度、膜形成條件及類似條件而定。換言之，膜形成表面之表面粗糙度可藉由形成塗層而劣化。在此狀況下，膜形成表面 (塗層表面）之表面粗糙度可藉由改良表面粗糙度但不產生新的凹缺陷之習知方法而改良。該等方法之特定實例較佳 125722.doc -24- 200830034 - 包括在低壓下機械拋光，稱為接觸拋光。又，可藉由控制 . 蝕刻速率及/或蝕刻時間而藉由應用濕式蝕刻或乾式蝕刻來改良表面粗韃度。當使用本發明之EUV光罩基底用基板來製造Euv光罩基底時，可藉由上述程序使用習知膜形成方法（詳言之，濺鍍法’諸如磁控濺鍍法或離子束濺鍍法）在所形成之塗層表面上以多層反射膜及吸收層之順序形成多層反射膜及吸收層。 • 夕私夕層反射膜不受特定限制，只要其具有Euv光罩基底之多層反射膜之所要特性。多層反射膜特定需要之特性為其係具有高EUV光反射率之膜。特定言之，當多層反射膜之表面以EUV光波長區之光照射時，波長13·5 nm附近之光反射率之最大值較佳為6〇%或更高，且更佳為65%或更滿足上述特性之多層反射膜之實例包括包含交替層壓之 φ Sl膜及Mo膜的Si/Mo多層反射膜、包。含交替層壓之以膜及After coating the solution containing the polyglycol compound, the substrate is heated and hardened in an oxygen-containing gas atmosphere or a water vapor gas atmosphere. As a result, the polycohering compound = reacts with oxygen or water vapor in a gaseous environment, and is converted into cerium oxide, which forms a cerium oxide coating (or a coating containing SW2 as a main backbone) on the film forming surface of the substrate. The oxygen-containing gas environment as used herein means that oxygen is present in a gaseous environment, and the oxygen concentration in the gaseous environment is not particularly limited. The water vapor gas environment used herein means that water vapor is present in the gaseous environment, and the water vapor concentration in the gaseous environment is not particularly limited. In this way, you can use yf亍 to heat and harden. The heating and hardening temperature varies depending on the type of polyazide compound used and the concentration of the polyazane compound in the solution, but heating and hardening are preferably carried out at a temperature of from MO to 5 °C. When the heating and hardening temperature is lower than ❹, the conversion of the polyazide compound to cerium oxide is insufficient, and thus the cerium oxide coating having a sufficient thickness to smooth the concave defects cannot be formed (or contains Si 〇 2 as Coating of the main backbone). When the heating and hardening temperature exceeds 5 〇 (rc, the baking (heating and hardening) temperature is higher than the strain point of the substrate (although depending on the substrate material), and thus the substrate may be deformed. The heating and hardening temperature is preferably 150 to 400 ° C. When a conversion reaction accelerator such as a catalyst or a polymerization initiator is used as described above, it is considered that hardening at a significant low temperature (for example, hardening at room temperature) is possible. Further, when UV radiation is applied, it is considered Hardening at room temperature is 125722.doc -23-200830034. Possible. - In the present invention, the film forming surface having the concave defect is formed on the film forming surface having the concave defect on the substrate for the Euv mask substrate. The oxidized stone coating (or the coating containing si〇2 as the main backbone) is especially considered to be smooth and the coating of the oxygen-cut coating is smoothed. The film is formed after the coating is formed. The surface of the yttrium oxide coating (or the coating containing Si〇2 as the main backbone). In the case of smoothing the surface of the film having the concave defect, the surface of the film (three) Φ (ie, the surface of the coating) does not have to be at all There is a concave In the case of trapping, it is sufficient to smooth only the concave defects existing on the surface of the coating so that the size of the substrate for the Euv mask substrate is not problematic. The size of the concave defect as a defect of the EUV mask base is concave. The shape of the defect varies and cannot be completely defined. As an approximation, when a concave defect having a depth of more than 3 nm exists on the film forming surface of the substrate, the surface of the multilayer reflective film or the absorbing layer formed on the film forming surface may be Concave defects occur, and defects can become defects of the EUV mask substrate. Even when concave defects are not present on the surface of the multilayer reflective φ film or the absorbing layer, structural perturbation in these films can cause phase defects. The depth of the concave defect existing on the surface of the coating layer is preferably 3 nm or less, and more preferably 1 nm or less. The surface of the coating layer may be formed on the surface of the substrate for the substrate of the EUV mask substrate, which may be defective. The surface roughness depends on the composition of the coating to be formed, the film thickness, the film formation conditions, and the like. In other words, the surface roughness of the film forming surface can be deteriorated by forming a coating layer. The surface roughness of the film forming surface (coating surface) can be improved by a conventional method of improving the surface roughness without generating new concave defects. Specific examples of the methods are preferably 125722.doc -24- 200830034 - Mechanical polishing at low pressure, referred to as contact polishing. Further, surface roughness can be improved by applying wet etching or dry etching by controlling the etching rate and/or etching time. When the EUV mask substrate is used to manufacture the Euv mask substrate, the conventional film formation method (in detail, sputtering method such as magnetron sputtering or ion beam sputtering) can be formed by the above procedure. A multilayer reflective film and an absorbing layer are formed on the surface of the coating in the order of a multilayer reflective film and an absorbing layer. • The smectic reflective film is not particularly limited as long as it has the desired characteristics of the multilayer reflective film of the Euv reticle substrate. The specific desirable properties of the multilayer reflective film are those which have a high EUV light reflectance. Specifically, when the surface of the multilayer reflective film is irradiated with light of an EUV light wavelength region, the maximum value of the light reflectance near the wavelength of 13.5 nm is preferably 6% or more, and more preferably 65% or Examples of the multilayer reflective film which more satisfies the above characteristics include a Si/Mo multilayer reflective film comprising a φ Sl film and a Mo film which are alternately laminated, and a package. Film with alternating lamination

Mo膜的Be/Mo多層反射膜、包含交替層壓之以化合物層及 Mo化合物層之Si化合物/Mo化合物多層反射膜、包含以以膜、Mo膜及Ru膜順序層壓之Si膜、M〇膜及Ru膜的 Si/Mo/Ru多層反射膜及包含以以膜、Ru膜、M〇m及如膜層壓之Si膜、Rii膜、Mo膜及RU膜的Si/Ru/M〇/Ru多層反射膜。用於膜形成多層反射膜之程序可為一般使用濺鍍法進行多層反射膜之膜形成的程序。舉例而言，當使用離子束濺 125722.doc -25- 200830034 : 鍍法形成以/]^0多層反射膜時，較佳使用Si靶材且使用Ar . 氣體（氣體壓力·· h3x10·2 Pa至2.7X10-2 Pa)作為濺鍍氣體在300至1，500 V之離子加速電壓下及〇〇3至〇3〇 nm/seCi 膜开y成速率下形成厚度為4.5 nm之y膜，且接著使用M〇^ ’ 材且使用Ar氣體（氣體壓力·· 1·3χ1(Γ2 Pa至2·7χ1(Γ2 Pa)作，為濺鍍氣體以300至l，500 v之離子加速電壓及〇〇3至〇.3〇 nm/sec之膜形成速率形成厚度為2.3 11111之]^〇膜。慮及前述 φ 程序為一個循環，以40至5〇個循環層壓Si膜及Mo膜。因此，形成Si/Mo多層反射膜。在形成多層反射膜時，膜形成較佳在使用基板用轉盤使基板旋轉的同時進行以獲得均一膜形成。為防止多層反射膜之表面氧化，多層反射膜之頂層較佳為包含難以氧化之材料的層。將包含難以氧化之材料的層用作多層反射膜之頂蓋層。包含難以氧化之材料的層之實例包括81層。當多層反射膜為Si/M〇膜時，可藉由以^層形 • 成頂層而將頂層用作頂蓋層。在此狀況下，頂蓋層之膜厚度較佳為11.0士 1.0 ηπι。在本說明書中，藉由上述程序形成於塗層表面上之具有多層反射膜的基板稱為"具有Euv光罩基底用多層反射膜之基板”。當藉由使用具有多層反射膜之基板來製造euv 光罩基底時，使用習知膜形成法（詳言之，濺鍍法，諸如磁控濺鍍法或離子束濺鍍法）在藉由上述程序形成之多層反射膜上形成吸收層，或形成（在多層反射膜之頂層為頂蓋層之狀況下）頂蓋層。、 125722.doc -26 - 200830034 構成开> 成於多層反射膜上之吸收層的材料之實例包括對 EUV光具有高吸收係數之材料，特定言之為Cr、Ta及其氮化物。其中，TaN為較佳的，因為TaN傾向於為非晶形的且其表面為平滑的。吸收層厚度較佳為50至100 nm。吸收層之膜形成方法不受特定限制，只要其為濺鍍法，且可為磁控濺鍍法或離子束濺鍍法中之任一者。當使用離子束濺鍍法形成作為吸收層之TaN層時，較佳使用丁 a|fc材且使用N2氣（氣體壓力：ι·3χ1〇-2 pa至2·7χ1〇-2 Pa)作為濺鍍氣體在300至ι，5〇〇 ν之電壓下及〇〇1至〇1 nm/seC之膜形成速率下形成厚度為50至l〇〇nm之膜。在使用濺鍍法膜形成吸收層時，較佳在使用基板用轉盤使基板旋轉的同時進行膜形成以獲得均一膜形成。可在多層反射膜與吸收層之間形成緩衝層。構成緩衝層之材料的實例包括Cr、A卜RU、Ta及其氮化物；且進一步包括Si〇2、ShN4及Al2〇3。緩衝層厚度較佳為1〇至6〇11111。實例將藉由參看以下實例而較詳細地說明本發明。在實例中，藉由旋塗法將含有聚矽氮烷化合物之溶液塗敷至EUV光罩基底用基板之表面，且在空氣中加熱及硬化從而在基板表面上形成氧化矽塗層。此程序中之各別條件如下。 EUV光罩基底用基板a Be/Mo multilayer reflective film of a Mo film, a Si compound/Mo compound multilayer reflective film comprising a compound layer and a Mo compound layer alternately laminated, and a Si film laminated in the order of a film, a Mo film, and a Ru film, M Si/Mo/Ru multilayer reflective film of ruthenium film and Ru film and Si/Ru/M〇 containing Si film, Rii film, Mo film and RU film laminated with film, Ru film, M〇m and film /Ru multilayer reflective film. The procedure for forming a multilayer reflective film for a film may be a procedure for forming a film of a multilayer reflective film by sputtering generally. For example, when ion beam sputtering 125722.doc -25-200830034: plating method is used to form a multilayer reflective film, it is preferable to use a Si target and use Ar gas (gas pressure··h3x10·2 Pa) To 2.7X10-2 Pa) as a sputtering gas, a y film having a thickness of 4.5 nm is formed at an ion acceleration voltage of 300 to 1,500 V and a film opening rate of 〇〇3 to 〇3〇nm/seCi, and Next, use M〇^' and use Ar gas (gas pressure ······························· Pa2 Pa to 2·7χ1(Γ2 Pa), for the sputtering gas with an ion acceleration voltage of 300 to 1,500 v and 〇〇 The film formation rate of 3 to 〇.3 〇 nm/sec is formed into a film having a thickness of 2.3 11111. Considering the aforementioned φ program as a cycle, the Si film and the Mo film are laminated in 40 to 5 cycles. The Si/Mo multilayer reflective film is formed. When the multilayer reflective film is formed, the film formation is preferably performed while rotating the substrate using the substrate with a turntable to obtain a uniform film formation. To prevent oxidation of the surface of the multilayer reflective film, the top layer of the multilayer reflective film A layer containing a material that is difficult to oxidize is preferred. A layer containing a material that is difficult to oxidize is used as the top of the multilayer reflective film. The cover layer. An example of a layer containing a material that is difficult to oxidize includes 81 layers. When the multilayer reflective film is a Si/M tantalum film, the top layer can be used as a cap layer by forming a top layer. The film thickness of the top cover layer is preferably 11.0 ± 1.0 ηπι. In the present specification, the substrate having the multilayer reflective film formed on the surface of the coating by the above procedure is called "multilayer reflection with Euv mask substrate a substrate for a film. When an euv mask substrate is fabricated by using a substrate having a multilayer reflective film, a conventional film formation method is used (in detail, sputtering, such as magnetron sputtering or ion beam sputtering) Forming an absorbing layer on the multilayer reflective film formed by the above procedure, or forming a cap layer (in the case where the top layer of the multilayer reflective film is a cap layer). 125722.doc -26 - 200830034 constituting opening > Examples of the material of the absorbing layer on the multilayer reflective film include materials having a high absorption coefficient for EUV light, specifically Cr, Ta and their nitrides. Among them, TaN is preferable because TaN tends to be amorphous And its surface is smooth. The thickness of the layer to be collected is preferably from 50 to 100 nm. The film formation method of the absorption layer is not particularly limited as long as it is a sputtering method, and may be any of magnetron sputtering or ion beam sputtering. When a TaN layer as an absorbing layer is formed by ion beam sputtering, it is preferred to use a butyl a|fc material and use N 2 gas (gas pressure: ι·3χ1〇-2 pa to 2·7χ1〇-2 Pa) as a sputtering. The gas is formed into a film having a thickness of 50 to 10 nm at a film formation rate of 300 to ι, 5 〇〇ν and a film formation rate of 〇〇1 to 〇1 nm/seC. When the absorption layer is formed using a sputtering method, it is preferred to perform film formation while rotating the substrate using a substrate with a turntable to obtain a uniform film formation. A buffer layer may be formed between the multilayer reflective film and the absorber layer. Examples of the material constituting the buffer layer include Cr, A, RU, Ta, and nitride thereof; and further include Si〇2, ShN4, and Al2〇3. The thickness of the buffer layer is preferably from 1 〇 to 6 〇 11111. EXAMPLES The invention will be described in more detail by reference to the following examples. In the examples, a solution containing a polyazide compound is applied to the surface of the substrate for an EUV reticle substrate by spin coating, and heated and hardened in the air to form a cerium oxide coating on the surface of the substrate. The individual conditions in this procedure are as follows. EUV reticle substrate

Si〇2-Ti02 糸統玻璃基板：Asahi Glass Co·，Ltd·之產品，零件編號6025 125722.doc •27- 200830034 . 使用經拋光以具有〇·15 nm或更低之表面粗糙度及100 nm 或更低之平坦度的基板。聚醯亞胺膠帶（kapton tape)黏附至基板表面之一部分。熱膨脹係數：υχΐίτ7/^ - 揚氏模數：67 GPaSi〇2-Ti02 玻璃 glass substrate: product of Asahi Glass Co., Ltd., part number 6025 125722.doc •27- 200830034 . Use polished to have a surface roughness of 15 nm or less and 100 nm Or lower flatness of the substrate. A kapton tape is adhered to a portion of the surface of the substrate. Thermal expansion coefficient: υχΐίτ7/^ - Young's modulus: 67 GPa

. 應變點 Ts : 1，100°C 尺寸：外形6忖（152.4 mm方形），厚度6.3 mm W 含有聚矽氮烷化合物之溶液名稱：ALCEDAR COAT NN310-20(Clariant (Japan) Κ·Κ· 之產品）數量平均分子量：900 溶劑：二曱苯聚矽氮烷化合物含量：20重量％密度：0.92(聚矽氮烷化合物含量為20重量％之目錄值） $ 黏度：1.10 cp(聚矽氮烷化合物含量為20重量％之目錄值）將上述溶液以二甲苯稀釋以將聚矽氮烷化合物含量調整 ’ 為10重量％、5重量％及2重量％。、旋塗濾紙：〇·5 μπι 旋塗條件：2,000 rpm，10 sec。在上述條件下，將2 cc含聚矽氮烷化合物之溶液旋塗於基板表面上。 125722.doc -28 - 200830034 加熱及硬化將旋塗後之基板置於清潔烘箱中，且在空氣中在200°C 下加熱且硬化歷時1小時。加熱且硬化後，自基板表面剝離聚醯亞胺膠帶，且以非 - 接觸三維表面形狀量測設備（Zygo NewView)量測其上膠帶 β 剝離區域（原始表面）與氧化矽塗層形成區域之間的高度差。因此，確認氧化矽塗層之膜厚度為150 nm(聚矽氮烷化合物含量：10重量％)、50 nm(聚矽氮烷化合物含量：5 ^ 重量％)及20 nm(聚矽氮烷化合物含量：2重量％)。此結果展示，可藉由改變溶液中之聚矽氮烷化合物含量來控制基板表面上形成之氧化矽塗層之膜厚度。提供具有與上述組合物相同之組合物的六個EUV光罩基底用基板，且藉由缺陷檢查工具檢查各別基板表面上之凹缺陷。在缺陷檢查工具偵測到之凹缺陷周圍給出維氏標記 (Vickers marking)，且藉由原子力顯微鏡（AFM)量測凹缺 ▲ 陷之形狀。所獲得之結果展示於下表1中。表1 凹缺陷(單位·· nm) 寬度(最小）寬度(最大）深度形狀凹缺陷1 145 156 22.1 坑凹缺陷2 108 242 14.5 坑凹缺陷3 100 203 12.5 坑凹缺陷4 98 294 8.4 坑凹缺陷5 83 268 20.2 坑凹缺陷6 102 229 6.4 坑 125722.doc -29 - 200830034 藉由與上述程序相同之程序藉由旋塗法將含有聚矽氮烷化口物（聚矽氮烷化合物含量：2重量％)之溶液塗敷至上文所提供之六個基板之表面，且加熱及硬化以在基板表面上形成氧化矽塗層。加熱及硬化後，試圖使用AFM量測氧化矽塗層表面上之凹缺陷之形狀。然而，將基板表面上存在斤有凹缺]^以氧化石夕塗層完全覆蓋，且其位置不可確涊。如表1中可見.，由AFM分析確認，藉由旋塗含有聚矽氮燒化合物（聚矽氮烷化合物含量：2重量％)之溶液，隨後藉由加熱且硬化使具有不同形狀之凹缺陷平滑且減少其深度以產生具有RMS(均方根）粗糙度之平滑表面（其展示為〇· 15 nm或更低的難以與基板的表面粗糙度相辨別的程度）’從而在基板表面上形成氧化石夕塗層。與上文所述類似’提供六個EUV光罩基底用基板，且藉由原子力顯微鏡 (AFM)量測缺陷檢查工具所偵測到之凹缺陷之形狀。所獲得之結果展示於下表2中。以與上述程序相同之程序藉由旋塗法將含有聚矽氮烷化合物（聚石夕氮烧化合物含量：〇·2重量％)之溶液塗敷至上文所提供之六個基板之表面，且加熱及硬化以在基板表面上形成氧化矽塗層。加熱及硬化後，藉由AFM量測氧化矽塗層表面上之凹缺陷之形狀。所獲得之結果展示於下表2 中。 125722.doc 30- 200830034 表2 凹缺陷(單位：nm) 氧化矽塗層形成之前氧化矽塗層形成之後寬度(最小）寬度(最大）深度形狀深度凹缺陷7 211 443 6.0 刮痕 5.2 凹缺陷8 130 463 4.7 刮痕 3.2 凹缺陷9 91 228 17.2 刮痕 8.4 凹缺陷10 89 190 16.1 坑 7.2 凹缺陷11 113 153 15.6 坑 8,9 凹缺陷12 99 165 12.0 坑 10.0 如表2中可見，根據本發明確認可平滑具有各種形狀之凹缺陷且其深度可減小。在表2中，形成氧化矽塗層後之凹缺陷之深度超過3 nm。然而，鑒於凹缺陷之寬度及形狀，可認為此等凹缺陷在EUV光罩基底製造中不具問題，因為此等凹缺陷可被平滑，且可藉由旋塗含有聚矽氮烷化合物（聚矽氮烷化合物含量：0.2重量％)之溶液，隨後以與上文所述之程序相同的程序加熱及硬化而於基板表面上再次形成氧化矽塗層，從而將其深度減小至AFM不可偵測之程度。圖1至圖3中展示凹缺陷10至12在氧化矽塗層形成之前及之後的AFM影像。圖1(a)為凹缺陷10在氧化矽塗層形成之前的AFM影像，且圖1(b)為凹缺陷10在氧化矽塗層形成之後的AFM影像。圖2(a)為凹缺陷11在氧化矽塗層形成之前的AFM影像，且圖2(b)為凹缺陷11在氧化矽塗層形成之後的 125722.doc -31- 200830034 • AFM影像。®3⑷為凹缺陷12在氧切塗層形成之前的 • AFM影像’且圖3(b)為凹缺陷12在氧切塗層形成之後的 AFM影像。如圖示中可見’根據本發明，具有各種形狀之凹缺陷可被平滑且其深度可減小而不引起新的凹缺陷，且 V 不使表面粗糙度顯著增加。 - 儘官已詳細且根據本發明之特定實施例描述本發明，熟習此項技術者顯然將可在不背離其精神及範嘴的情況下對籲本發明作出各種改變及修正。本申清案係基於2006年1〇月13曰申請之曰本專利申請案第2006-280173號，且其内容以引用的方式併入本文中。【圖式簡單說明】圖1(a)為在凹缺陷10上形成氧化矽塗層前之AFM影像，且圖1(b)為在凹面1〇上形成氧化矽塗層後之AFM影像。圖2(a)為在凹缺陷1!上形成氧化矽塗層前之afm影像，且圖2(b)為在凹面11上形成氧化矽塗層後之AFM影像。 φ 圖3(a)為在凹缺陷12上形成氧化矽塗層前之AFM影像，且圖3(b)為在凹面12上形成氧化矽塗層後之afm影像。 125722.doc 32-Strain point Ts: 1,100°C Dimensions: 6忖 (152.4 mm square), 6.3 mm thick W Solution containing polyazide compound Name: ALCEDAR COAT NN310-20 (Clariant (Japan) Κ·Κ· Product) Amount of the average molecular weight: 900 Solvent: Diterpene benzene polyazane content: 20% by weight Density: 0.92 (Catalogue value of polyoxazane compound content: 20% by weight) $ Viscosity: 1.10 cp (polyazane) The content of the compound was 20% by weight. The above solution was diluted with xylene to adjust the polyazinane compound content to 10% by weight, 5% by weight and 2% by weight. , Spin coating Filter paper: 〇·5 μπι Spin coating conditions: 2,000 rpm, 10 sec. Under the above conditions, 2 cc of a solution containing a polyazide compound was spin-coated on the surface of the substrate. 125722.doc -28 - 200830034 Heating and hardening The spin-coated substrate was placed in a clean oven and heated in air at 200 ° C for 1 hour. After heating and hardening, the polyimide tape was peeled off from the surface of the substrate, and the band β peeling region (original surface) and the yttrium oxide coating forming region were measured by a non-contact three-dimensional surface shape measuring device (Zygo New View). The difference in height between the two. Therefore, it was confirmed that the film thickness of the yttrium oxide coating was 150 nm (polyazide compound content: 10% by weight), 50 nm (polyazide compound content: 5% by weight), and 20 nm (polyazide compound). Content: 2% by weight). This result shows that the film thickness of the cerium oxide coating formed on the surface of the substrate can be controlled by changing the content of the polyazane compound in the solution. Six EUV reticle substrate substrates having the same composition as the above composition were provided, and the defects on the surfaces of the respective substrates were inspected by a defect inspection tool. The Vickers marking is given around the concave defect detected by the defect inspection tool, and the shape of the concave ▲ is measured by an atomic force microscope (AFM). The results obtained are shown in Table 1 below. Table 1 Concave defects (unit · · nm) Width (minimum) Width (maximum) Depth shape concave defect 1 145 156 22.1 Pit defect 2 108 242 14.5 Pit defect 3 100 203 12.5 Pit defect 4 98 294 8.4 Pit defect 5 83 268 20.2 Pit-concave defects 6 102 229 6.4 Pit 125722.doc -29 - 200830034 The content of polyazide-containing compounds (polyazapine compound content: 2 by spin coating) by the same procedure as the above procedure A solution of % by weight) was applied to the surface of the six substrates provided above and heated and hardened to form a yttrium oxide coating on the surface of the substrate. After heating and hardening, an attempt was made to measure the shape of the concave defect on the surface of the ruthenium oxide coating using AFM. However, there is a dent in the surface of the substrate, which is completely covered by the oxidized stone coating, and its position is not correct. As can be seen from Table 1, it was confirmed by AFM analysis that a solution containing a polyfluorene-sinter compound (polyazide compound content: 2% by weight) was spin-coated, followed by heating and hardening to have concave defects having different shapes. Smoothing and reducing its depth to produce a smooth surface with RMS (root mean square) roughness (which is shown to be 〇·15 nm or less difficult to distinguish from the surface roughness of the substrate)' to form on the substrate surface Oxide oxide coating. A substrate for six EUV reticle substrates was provided similarly as described above, and the shape of the concave defect detected by the defect inspection tool was measured by an atomic force microscope (AFM). The results obtained are shown in Table 2 below. Applying a solution containing a polyazide compound (the content of polysulfide compound: 2% by weight) to the surface of the six substrates provided above by spin coating in the same procedure as the above procedure, and Heating and hardening to form a yttria coating on the surface of the substrate. After heating and hardening, the shape of the concave defect on the surface of the ruthenium oxide coating was measured by AFM. The results obtained are shown in Table 2 below. 125722.doc 30- 200830034 Table 2 Concave defects (unit: nm) yttrium oxide coating before formation of yttrium oxide coating after formation width (minimum) width (maximum) depth shape depth concave defect 7 211 443 6.0 scratch 5.2 concave defect 8 130 463 4.7 Scratch 3.2 Concave defect 9 91 228 17.2 Scratch 8.4 Concave defect 10 89 190 16.1 Pit 7.2 Concave defect 11 113 153 15.6 Pit 8, 9 Concave defect 12 99 165 12.0 Pit 10.0 As can be seen in Table 2, according to the invention It is confirmed that the concave defects having various shapes can be smoothed and the depth thereof can be reduced. In Table 2, the depth of the concave defects after the formation of the yttrium oxide coating exceeds 3 nm. However, in view of the width and shape of the concave defects, it is considered that such concave defects are not problematic in the manufacture of the EUV mask substrate because the concave defects can be smoothed and can be spin-coated with a polyazide compound (polyfluorene) a solution of a nitane compound content: 0.2% by weight), followed by heating and hardening in the same procedure as described above to form a yttria coating on the surface of the substrate again, thereby reducing the depth to AFM undetectable The extent of it. An AFM image of the concave defects 10 to 12 before and after the formation of the yttrium oxide coating is shown in Figs. Fig. 1(a) is an AFM image of the concave defect 10 before the yttrium oxide coating is formed, and Fig. 1(b) is an AFM image of the concave defect 10 after the yttrium oxide coating is formed. Fig. 2(a) is an AFM image of the concave defect 11 before the yttrium oxide coating is formed, and Fig. 2(b) is a 125142.doc -31-200830034 • AFM image of the concave defect 11 after the yttrium oxide coating is formed. ® 3 (4) is the AFM image of the concave defect 12 before the formation of the oxygen-cut coating and FIG. 3 (b) is the AFM image of the concave defect 12 after the formation of the oxygen-cut coating. As seen in the figure, according to the present invention, concave defects having various shapes can be smoothed and their depth can be reduced without causing new concave defects, and V does not cause a significant increase in surface roughness. The present invention has been described in detail with reference to the particular embodiments of the present invention, and it is obvious that those skilled in the art can make various changes and modifications of the present invention without departing from the spirit and scope of the invention. The present application is based on the present patent application No. 2006-280173, filed on Jan. 13, 2006, the content of which is hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(a) is an AFM image before a yttrium oxide coating is formed on a concave defect 10, and Fig. 1(b) is an AFM image after a yttrium oxide coating is formed on a concave surface 〇. 2(a) is an afm image before the yttrium oxide coating is formed on the concave defect 1!, and FIG. 2(b) is an AFM image after the yttrium oxide coating is formed on the concave surface 11. φ Figure 3(a) shows the AFM image before the yttrium oxide coating is formed on the concave defect 12, and Fig. 3(b) shows the afm image after the yttrium oxide coating is formed on the concave surface 12. 125722.doc 32-

Claims

200830034 十、申請專利範圍： 1. 一種用於EUV微影之反射式光罩基底（mask blank)用基板表面之平滑方法，其包含將含有聚矽氮烷化合物之溶液塗敷於具有凹缺陷之基板表面，且加熱及硬化該塗敷之 . 溶液以形成氧化矽塗層（包含Si02作為主骨幹之塗層），藉此平滑具有凹缺陷之基板表面。 2. 如請求項1之用於EUV微影之反射式光罩基底用基板表面之平滑方法，其中該含有聚矽氮烷化合物之溶液具有籲 0.05至2重量％之聚矽氮烷化合物濃度。 3. 如請求項1或2之用於EUV微影之反射式光罩基底用基板表面之平滑方法，其中該加熱及該硬化係在150至500°C 之溫度下在含氧氣體環境或含水蒸氣氣體環境中進行。 4. 如請求項1至3中任一項之用於EUV微影之反射式光罩基底用基板表面之平滑方法，其中在基板表面上之該等凹缺陷具有3 0 nm或更小之深度。 5. 如請求項1至4中任一項之用於EUV微影之反射式光罩基 ^ 底用基板表面之平滑方法，其中該等凹缺陷在加熱及硬化後具有3 nm或更小之深度。一 6· —種用於EUV微影之反射式光罩基底用基板，其具有以 * 如請求項1至5中任一項之方法平滑後之表面。 7. 一種用於EUV微影之具多層反射膜之基板，其包含如請求項6之用於EUV微影之反射式光罩基底用基板。 8. —種用於EUV微影之反射式光罩基底，其包含如請求項 6之用於EUV微影之反射式光罩基底用基板。 125722.doc 200830034 七、指定代表圖： * (一)本案指定代表圖為：第（1)圖。 _ (二)本代表圖之元件符號簡單說明： (無元件符號說明）八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無）200830034 X. Patent Application Range: 1. A method for smoothing the surface of a substrate for a reflective blank for EUV lithography, comprising applying a solution containing a polyazide compound to a concave defect The surface of the substrate is heated and hardened to form a yttrium oxide coating (including a coating of SiO 2 as a main backbone), thereby smoothing the surface of the substrate having concave defects. 2. The method of smoothing the surface of a substrate for a reflective reticle substrate for EUV lithography according to claim 1, wherein the solution containing the polyazide compound has a polyazinane compound concentration of 0.05 to 2% by weight. 3. The method of smoothing the surface of a substrate for a reflective reticle substrate for EUV lithography according to claim 1 or 2, wherein the heating and the hardening are in an oxygen-containing gas atmosphere or water at a temperature of 150 to 500 °C. It is carried out in a vapor gas atmosphere. 4. The method of smoothing the surface of a substrate for a reflective reticle substrate for EUV lithography according to any one of claims 1 to 3, wherein the concave defects on the surface of the substrate have a depth of 30 nm or less . 5. The method of smoothing the surface of a substrate for a reflective reticle for EUV lithography according to any one of claims 1 to 4, wherein the concave defects have a thickness of 3 nm or less after heating and hardening. depth. A substrate for a reflective reticle substrate for EUV lithography, which has a surface smoothed by the method of any one of claims 1 to 5. A substrate having a multilayer reflective film for EUV lithography, comprising the substrate for a reflective reticle substrate for EUV lithography according to claim 6. 8. A reflective reticle substrate for EUV lithography comprising the substrate for a reflective reticle substrate for EUV lithography of claim 6. 125722.doc 200830034 VII. Designated representative map: * (1) The representative representative of the case is: (1). _ (2) Simple description of the symbol of the representative figure: (No description of the symbol of the component) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none)

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