TWI704220B - Surface treatment agent and surface treatment method - Google Patents

Surface treatment agent and surface treatment method Download PDF

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TWI704220B
TWI704220B TW105130432A TW105130432A TWI704220B TW I704220 B TWI704220 B TW I704220B TW 105130432 A TW105130432 A TW 105130432A TW 105130432 A TW105130432 A TW 105130432A TW I704220 B TWI704220 B TW I704220B
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surface treatment
nitrogen
hydrogen atom
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TW201726905A (en
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森大二郎
熊澤明
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日商東京應化工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

本發明之目的在於提供一種可有效地防止設置於基板上之無機圖案或樹脂圖案之圖案崩塌的表面處理劑；及使用此種表面處理劑之表面處理方法。又，作為其他目的，本發明之目的在於提供一種可對被處理體之表面高度地進行矽烷基化處理之表面處理劑；及使用此種表面處理劑之表面處理方法。 本發明使用一種表面處理劑，其係用於被處理體之表面處理者，且含有矽烷基化劑、及不包含矽原子之含氮雜環化合物。The object of the present invention is to provide a surface treatment agent which can effectively prevent the pattern of the inorganic pattern or the resin pattern provided on the substrate from collapsing; and a surface treatment method using the surface treatment agent. In addition, as another object, the object of the present invention is to provide a surface treatment agent capable of highly silylating the surface of an object to be treated; and a surface treatment method using this surface treatment agent. The present invention uses a surface treatment agent, which is used for the surface treatment of the object to be treated, and contains a silylation agent and a nitrogen-containing heterocyclic compound that does not contain silicon atoms.

Description

表面處理劑及表面處理方法Surface treatment agent and surface treatment method

本發明係關於一種表面處理劑及表面處理方法，尤其關於一種可較佳地應用於半導體積體電路製造中所使用之基板等被處理體之表面處理之表面處理劑及表面處理方法。The present invention relates to a surface treatment agent and a surface treatment method, and more particularly to a surface treatment agent and a surface treatment method that can be preferably applied to the surface treatment of substrates used in the manufacture of semiconductor integrated circuits.

於半導體裝置等之製造中，於對基板實施蝕刻等處理之前使用微影技術。於該微影技術中，使用感光性樹脂組合物於基板上設置感光性樹脂層，繼而，將其藉由活性放射線選擇性地進行照射而進行曝光，進行顯影處理後，選擇性地溶解去除感光性樹脂層，於基板上形成樹脂圖案。然後，以該樹脂圖案作為遮罩進行蝕刻處理，藉此於基板形成無機圖案。 另外，近年來，半導體裝置之高積體化、微小化之傾向提高，從而進行成為遮罩之樹脂圖案、或藉由蝕刻處理所製作之無機圖案之微細化、高縱橫比化。但是，另一方面，產生所謂圖案崩塌之問題。該圖案崩塌係於在基板上並列形成多數之樹脂圖案或無機圖案時，鄰接之圖案彼此以相互倚靠之方式接近，根據情況，圖案自基部折損或剝離之現象。若產生此種圖案崩塌，則無法獲得所需之製品，故而引起製品之良率或可靠性之降低。 可知該圖案崩塌係於圖案形成後之清洗處理中，於乾燥清洗液時，因該清洗液之表面張力而產生。即，於在乾燥過程中去除清洗液時，於圖案間基於清洗液之表面張力之應力發揮作用，產生圖案崩塌。 因此，迄今為止多次進行於清洗液中添加使表面張力降低之物質，防止圖案崩塌之嘗試。例如，提出一種添加有異丙醇之清洗液、或添加有氟系界面活性劑之清洗液等(例如參照專利文獻1、2)。 又，與圖案崩塌不同，為了提昇成為遮罩之樹脂圖案與基板之表面之密接性，防止因化學顯影液所引起之樹脂圖案之一部分損耗，於在基板設置感光性樹脂層之前，對基板之表面進行使用六甲基二矽氮烷(HMDS)之疏水化處理(矽烷基化處理)(例如參照專利文獻3之「先前技術」)。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開平6-163391號公報 [專利文獻2]日本專利特開平7-142349號公報 [專利文獻3]日本專利特表平11-511900號公報In the manufacture of semiconductor devices, etc., lithography technology is used before processing such as etching the substrate. In this lithography technology, a photosensitive resin layer is provided on a substrate using a photosensitive resin composition, and then the photosensitive resin layer is selectively irradiated with active radiation to be exposed, and after developing treatment, the photosensitive resin layer is selectively dissolved and removed. The resin layer forms a resin pattern on the substrate. Then, etching is performed using the resin pattern as a mask, thereby forming an inorganic pattern on the substrate. In addition, in recent years, there has been an increasing trend towards higher integration and miniaturization of semiconductor devices, and resin patterns used as masks or inorganic patterns produced by etching treatment have been refined and increased in aspect ratio. However, on the other hand, there is a problem of so-called pattern collapse. The pattern collapse is a phenomenon that when a large number of resin patterns or inorganic patterns are formed side by side on the substrate, adjacent patterns approach each other in a mutually leaning manner, and depending on the situation, the pattern is broken or peeled off from the base. If such pattern collapse occurs, the desired product cannot be obtained, which causes a decrease in product yield or reliability. It can be seen that the pattern collapse is caused by the surface tension of the cleaning solution during the cleaning process after the pattern is formed. That is, when the cleaning liquid is removed during the drying process, the stress based on the surface tension of the cleaning liquid between the patterns acts to cause pattern collapse. Therefore, many attempts have been made to prevent the pattern from collapsing by adding substances that reduce the surface tension to the cleaning solution. For example, a cleaning solution containing isopropanol or a cleaning solution containing a fluorine-based surfactant has been proposed (for example, refer to Patent Documents 1 and 2). In addition, unlike pattern collapse, in order to improve the adhesion between the resin pattern used as a mask and the surface of the substrate, and to prevent a part of the resin pattern from being lost due to chemical developer, before the photosensitive resin layer is placed on the substrate, the substrate The surface is subjected to hydrophobization treatment (silylation treatment) using hexamethyldisilazane (HMDS) (for example, refer to "Prior Art" of Patent Document 3). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 6-163391 [Patent Document 2] Japanese Patent Laid-Open No. 7-142349 [Patent Document 3] Japanese Patent Laid-Open No. 11-511900 Bulletin

[發明所欲解決之問題] 然而，於如專利文獻1、2中所記載之清洗液之處理中，存在圖案崩塌之防止不充分之問題。又，於藉由HMDS對基板等被處理體之表面實施矽烷基化處理之情形時，有矽烷基化處理需要時間，或被處理體之表面之矽烷基化處理不充分，故而無法獲得所需之效果之情形。 本發明係鑒於以上之情況而完成者，其目的在於提供一種可有效地防止設置於基板上之無機圖案或樹脂圖案之圖案崩塌之表面處理劑；及使用此種表面處理劑之表面處理方法。又，作為其他目的，本發明之目的在於提供一種可對被處理體之表面高度地進行矽烷基化處理之表面處理劑；及使用此種表面處理劑之表面處理方法。 [解決問題之技術手段] 本發明者等人為了解決上述問題而反覆進行努力研究。其結果發現：若使用含有矽烷基化劑、及不包含矽原子之含氮雜環化合物之表面處理劑，對被處理體之表面進行表面處理，則被處理體之表面高度地疏水化。而且發現：尤其是藉由此種表面處理劑對設置於基板上之無機圖案或樹脂圖案之表面進行處理而進行疏水化，提高對清洗液之接觸角，藉此防止該等無機圖案或樹脂圖案之圖案崩塌，從而完成本發明。具體而言，本發明提供如下所述者。 本發明之第一態樣係一種表面處理劑，其係用於被處理體之表面處理者，且包含矽烷基化劑、及不包含矽原子之含氮雜環化合物。 本發明之第二態樣係一種表面處理方法，其係使第一態樣之表面處理劑暴露於被處理體之表面，對基板之表面進行處理。 [發明之效果] 根據本發明，提供一種可有效地防止設置於基板上之無機圖案或樹脂圖案之圖案崩塌之表面處理劑；及使用此種表面處理劑之表面處理方法。又，根據本發明，提供一種可對被處理體之表面高度地進行矽烷基化處理之表面處理劑；及使用此種表面處理劑之表面處理方法。[Problem to be Solved by the Invention] However, in the treatment of the cleaning liquid as described in Patent Documents 1 and 2, there is a problem that the prevention of pattern collapse is insufficient. In addition, when using HMDS to perform silylation treatment on the surface of a substrate, etc., the silylation treatment may take time, or the silylation treatment on the surface of the object may not be sufficient. The effect of the situation. The present invention was completed in view of the above circumstances, and its purpose is to provide a surface treatment agent that can effectively prevent the pattern of inorganic patterns or resin patterns provided on a substrate from collapsing; and a surface treatment method using this surface treatment agent. In addition, as another object, the object of the present invention is to provide a surface treatment agent capable of highly silylating the surface of an object to be treated; and a surface treatment method using this surface treatment agent. [Technical Means to Solve the Problem] The inventors of the present invention have repeatedly studied hard to solve the above-mentioned problems. As a result, it was found that if a surface treatment agent containing a silylation agent and a nitrogen-containing heterocyclic compound containing no silicon atoms is used to surface treatment the surface of the object to be treated, the surface of the object to be treated is highly hydrophobized. Moreover, it was found that, in particular, the surface of the inorganic pattern or resin pattern provided on the substrate is treated by this surface treatment agent to make the surface of the inorganic pattern or resin pattern hydrophobized to increase the contact angle of the cleaning liquid, thereby preventing the inorganic pattern or resin pattern The pattern collapsed, thus completing the present invention. Specifically, the present invention provides those described below. The first aspect of the present invention is a surface treatment agent which is used for the surface treatment of the object to be treated and contains a silylation agent and a nitrogen-containing heterocyclic compound that does not contain silicon atoms. The second aspect of the present invention is a surface treatment method in which the surface treatment agent of the first aspect is exposed to the surface of the object to be processed to treat the surface of the substrate. [Effects of the Invention] According to the present invention, there is provided a surface treatment agent that can effectively prevent the pattern of an inorganic pattern or a resin pattern provided on a substrate from collapsing; and a surface treatment method using the surface treatment agent. In addition, according to the present invention, there is provided a surface treatment agent capable of highly silylating the surface of an object to be treated; and a surface treatment method using the surface treatment agent.

＜表面處理劑＞ 對表面處理劑進行說明。表面處理劑係於將被處理體之表面進行矽烷基化時使用。被處理體之種類並無特別限定。作為被處理體，較佳為「基板」。此處，作為成為矽烷基化處理之對象之「基板」，可例示為了製作半導體裝置而使用之基板，「基板之表面」除基板本身之表面以外，亦可例示：設置於基板上之無機圖案及樹脂圖案之表面；以及未圖案化之無機層及有機層之表面。 作為設置於基板上之無機圖案，可例示藉由利用光阻劑法於存在於基板之無機層之表面製作蝕刻遮罩，其後，進行蝕刻處理而形成之圖案。作為無機層，除基板本身以外，亦可例示構成基板之元素之氧化膜；形成於基板之表面之氮化矽、氮化鈦、鎢等無機物之膜或層等。作為此種膜或層，並無特別限定，可例示半導體裝置之製作過程中所形成之無機物之膜或層等。 作為設置於基板上之樹脂圖案，可例示藉由光阻劑法形成於基板上之樹脂圖案。此種樹脂圖案例如藉由於基板上形成作為光阻劑之膜之有機層，通過光罩對該有機層進行曝光、顯影而形成。作為有機層，除基板本身之表面以外，亦可例示設置於基板之表面所設置之積層膜之表面等者。作為此種有機層，並無特別限定，可例示於半導體裝置之製作過程中，為了形成蝕刻遮罩而設置之有機物之膜。 可藉由例如旋轉塗佈法或浸漬法等方法將添加有溶劑之溶液類型之表面處理劑塗佈於基板等被處理體之表面而進行表面處理。 本發明之表面處理劑包含矽烷基化劑、及不包含矽原子之含氮雜環化合物(以下，亦記載為雜環化合物)。以下，對各成分進行說明。 [矽烷基化劑] 首先，對本發明之表面處理劑中所使用之矽烷基化劑進行說明。本發明之表面處理劑中所使用之矽烷基化劑係用以將被處理體之表面進行矽烷基化，使被處理體之表面之疏水性較大之成分。 作為本發明之表面處理劑中所含有之矽烷基化劑，並無特別限定，可使用先前公知之所有矽烷基化劑。作為此種矽烷基化劑，例如可使用具有下述通式(2)所表示之取代基之矽烷基化劑或環狀矽氮烷化合物。 [化1]

Figure 02_image001
(上述通式(2)中，R4 、R5 及R6 分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R4 、R5 及R6 中所包含之碳原子之合計之個數為1個以上) 作為具有上述通式(2)所表示之取代基之矽烷基化劑，更具體而言，可使用下述通式(3)～(8)所表示之矽烷基化劑。 [化2]
Figure 02_image003
(上述通式(3)中，R4 、R5 及R6 係與上述通式(2)相同，R7 表示氫原子、或者飽和或不飽和烷基，R8 表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或者飽和或不飽和雜環烷基。R7 及R8 可相互鍵結而形成包含氮原子之環結構) [化3]
Figure 02_image005
(上述通式(4)中，R4 、R5 及R6 係與上述通式(2)相同，R9 表示氫原子、甲基、三甲基矽烷基或二甲基矽烷基，R10 、R11 及R12 分別獨立地表示氫原子或有機基，R10 、R11 及R12 中所包含之碳原子之合計之個數為1個以上) [化4]
Figure 02_image007
(上述通式(5)中，R4 、R5 及R6 係與上述通式(2)相同，X表示O、CHR14 、CHOR14 、CR14 R14 或NR15 ，R13 及R14 分別獨立地表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、三烷基矽烷基、三烷基矽烷氧基、烷氧基、苯基、苯基乙基或乙醯基，R15 表示氫原子、烷基或三烷基矽烷基) [化5]
Figure 02_image009
(上述通式(6)中，R4 、R5 及R6 係與上述通式(2)相同，R9 係與上述通式(4)相同，R16 表示氫原子、飽和或不飽和烷基、三氟甲基或三烷基矽烷基胺基) [化6]
Figure 02_image011
(上述通式(7)中，R17 及R18 分別獨立地表示氫原子、烷基、三烷基矽烷基，R17 及R18 中之至少一者表示三烷基矽烷基) [化7]
Figure 02_image013
(上述通式(8)中，R19 表示三烷基矽烷基，R20 及R21 分別獨立地表示氫原子或有機基) [化8]
Figure 02_image015
(上述通式(9)中，R4 、R5 及R6 係與上述通式(2)相同，R22 表示有機基，R23 不存在，或者於存在之情形時，表示-SiR24 R25 R26 。R24 、R25 及R26 分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R24 、R25 及R26 中之任一者可經由氮原子與R4 、R5 及R6 中之任一者進行鍵結而形成亞胺基) 作為上述式(3)所表示之矽烷基化劑，可列舉：N,N-二甲基胺基三甲基矽烷、N,N-二甲基胺基二甲基矽烷、N,N-二甲基胺基單甲基矽烷、N,N-二乙基胺基三甲基矽烷、第三丁基胺基三甲基矽烷、烯丙基胺基三甲基矽烷、三甲基矽烷基乙醯胺、N,N-二甲基胺基二甲基乙烯基矽烷、N,N-二甲基胺基二甲基丙基矽烷、N,N-二甲基胺基二甲基辛基矽烷、N,N-二甲基胺基二甲基苯基乙基矽烷、N,N-二甲基胺基二甲基苯基矽烷、N,N-二甲基胺基二甲基-第三丁基矽烷、N,N-二甲基胺基三乙基矽烷、三甲基矽烷胺、單甲基矽烷基咪唑、二甲基矽烷基咪唑、三甲基矽烷基咪唑、單甲基矽烷基三唑、二甲基矽烷基三唑、三甲基矽烷基三唑等。 作為上述式(4)所表示之矽烷基化劑，可列舉：六甲基二矽氮烷、N-甲基六甲基二矽氮烷、1,1,3,3-四甲基二矽氮烷、1,3-二甲基二矽氮烷、1,2-二-N-辛基四甲基二矽氮烷、1,2-二乙烯基四甲基二矽氮烷、七甲基二矽氮烷、九甲基三矽氮烷、三(二甲基矽烷基)胺、三(三甲基矽烷基)胺、五甲基乙基二矽氮烷、五甲基乙烯基二矽氮烷、五甲基丙基二矽氮烷、五甲基苯基乙基二矽氮烷、五甲基-第三丁基二矽氮烷、五甲基苯基二矽氮烷、三甲基三乙基二矽氮烷等。 作為上述式(5)所表示之矽烷基化劑，可列舉：乙酸三甲基矽烷酯、乙酸二甲基矽烷酯、乙酸單甲基矽烷酯、丙酸三甲基矽烷酯、丁酸三甲基矽烷酯、三甲基矽烷氧基-3-戊烯-2-酮等。 作為上述式(6)所表示之矽烷基化劑，可列舉：雙(三甲基矽烷基)脲、N-三甲基矽烷基乙醯胺、N-甲基-N-三甲基矽烷基三氟乙醯胺等。 作為上述式(7)所表示之化合物，可列舉：雙(三甲基矽烷基)三氟乙醯胺等，作為上述式(8)所表示之化合物，可列舉：2-三甲基矽烷氧基戊-2-烯-4-酮等。作為上述式(9)所表示之化合物，可列舉：1,2-雙(二甲基氯矽烷基)乙烷、第三丁基二甲基氯矽烷等。 作為環狀矽氮烷化合物，可列舉：2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷、2,2,6,6-四甲基-2,6-二矽-1-氮雜環己烷等環狀二矽氮烷化合物；2,2,4,4,6,6-六甲基環三矽氮烷、2,4,6-三甲基-2,4,6-三乙烯基環三矽氮烷等環狀三矽氮烷化合物；2,2,4,4,6,6,8,8-八甲基環四矽氮烷等環狀四矽氮烷化合物等。 此處，若注目於鍵結於矽原子之取代基，則較佳為使用該取代基中所包含之碳原子數較大之所謂龐大之取代基鍵結於矽原子之矽烷基化劑。藉由表面處理劑含有此種矽烷基化劑，可使藉由該表面處理劑受到處理之被處理體之表面之疏水性較大。於被處理體為基板之情形時，藉此，可提昇受到處理之基板之表面與樹脂圖案之間的密接性。又，如下文所說明般，於受到處理之基板之表面中，尤其是無機圖案或樹脂圖案之表面之疏水性變大，藉此可防止無機圖案或樹脂圖案之圖案崩塌。 因此，較佳為於上述通式(2)中，R4 、R5 及R6 中所包含之碳原子之合計之個數為3個以上。其中，就於矽烷基化反應中獲得充分之反應性之觀點而言，更佳為於上述通式(2)中，R4 、R5 及R6 中之任一者為碳原子數2個以上之有機基(以下，於該段落中，稱為「特定有機基」)，其餘2個分別獨立地為甲基或乙基。作為特定有機基，可例示：支鏈及/或可具有取代基之碳原子數2～20之烷基；可具有取代基之乙烯基；可具有取代基之芳基等。特定有機基之碳原子數更佳為2～12，進而較佳為2～10，尤佳為2～8。 就此種觀點而言，於上述所例示之矽烷基化劑中，可較佳地例示：N,N-二甲基胺基二甲基乙烯基矽烷、N,N-二甲基胺基二甲基丙基矽烷、N,N-二甲基胺基二甲基辛基矽烷、N,N-二甲基胺基二甲基苯基乙基矽烷、N,N-二甲基胺基二甲基苯基矽烷、N,N-二甲基胺基二甲基-第三丁基矽烷、N,N-二甲基胺基三乙基矽烷、N,N-二甲基胺基三甲基矽烷、五甲基乙基二矽氮烷、五甲基乙烯基二矽氮烷、五甲基丙基二矽氮烷、五甲基苯基乙基二矽氮烷、五甲基-第三丁基二矽氮烷、五甲基苯基二矽氮烷、三甲基三乙基二矽氮烷等。 上述所例示之矽烷基化劑可單獨使用或混合2種以上而使用。 [雜環化合物] 表面處理劑包含不包含矽原子之含氮雜環化合物(亦簡稱為雜環化合物)。 迄今為止，基板等被處理體之表面之矽烷基化有如下情形：例如於以六甲基二矽氮烷(HMDS)作為矽烷基化劑之情形時，矽烷基化劑之反應性不充分，故而矽烷基化反應需要較多之時間，或無法獲得被處理體之表面之充分之疏水性。 但是，於表面處理劑包含矽烷基化劑、及不包含矽原子之含氮雜環化合物之情形時，利用矽烷基化劑之矽烷基化反應藉由含氮雜環化合物之觸媒作用而促進，被處理體之表面高度地疏水化。 因此，若使用本發明之表面處理劑進行被處理體之表面之矽烷基化處理，則可高度地將被處理體之表面進行疏水化。又，若使用本發明之表面處理劑，對被處理體之表面進行與迄今為止相同程度之疏水化，則可縮短表面處理所需之時間。 雜環化合物只要為不包含矽原子，且於環結構中包含氮原子之化合物則並無特別限定。雜環化合物可於環中包含氧原子、硫原子等氮原子以外之雜原子。 雜環化合物較佳為包含具有芳香性之含氮雜環之化合物。藉由雜環化合物包含具有芳香性之含氮雜環，可使經表面處理劑處理之被處理體之表面之疏水性增大。 雜環化合物可為2個以上之複數個環藉由單鍵或二價以上之多價連結基進行鍵結而成之化合物。於此情形時，藉由連結基而鍵結之2個以上之複數個環包含至少一個含氮雜環即可。 於多價連結基中，就環彼此之位阻較小之方面而言，較佳為二價連結基。作為二價連結基之具體例，可列舉：碳原子數1～6之伸烷基、-CO-、-CS-、-O-、-S-、-NH-、-N=N-、-CO-O-、-CO-NH-、-CO-S-、-CS-O-、-CS-S-、-CO-NH-CO-、-NH-CO-NH-、-SO-及-SO2 -等。 就容易製備均勻之表面處理劑之方面而言，2個以上之複數個環藉由多價連結基進行鍵結而成之化合物中所包含之環的數量較佳為4以下，更佳為3以下，最佳為2。再者，例如關於萘環之類之縮合環，將環之數量設為2。 雜環化合物亦可為2個以上之複數個環進行縮合而成之含氮雜環化合物。於此情形時，構成縮合環之環中之至少一個環為含氮雜環即可。 就容易製備均勻之表面處理劑之方面而言，2個以上之複數個環進行縮合而成之含氮雜環化合物中所包含之環的數量較佳為4以下，較佳為3以下，最佳為2。 就使用表面處理劑之表面處理之效果較為良好之方面而言，雜環化合物較佳為包含含氮5員環、或包含含氮5員環骨架之縮合多環。 作為雜環化合物之較佳之例，例如可列舉：吡啶、嗒
Figure 105130432-A0304-12-0020-4
、吡
Figure 105130432-A0304-12-0020-4
、嘧啶、三
Figure 105130432-A0304-12-0020-4
、四
Figure 105130432-A0304-12-0020-4
、吡咯、吡唑、咪唑、三唑、四唑、
Figure 105130432-A0304-12-0015-1
唑、異
Figure 105130432-A0304-12-0015-1
唑、噻唑、異噻唑、
Figure 105130432-A0304-12-0015-1
二唑、噻二唑、喹啉、異喹啉、
Figure 105130432-A0304-12-xxxx-6
啉、酞
Figure 105130432-A0304-12-0020-4
、喹
Figure 105130432-A0304-12-0015-1
啉、喹唑啉、吲哚、吲唑、苯并咪唑、苯并三唑、苯并
Figure 105130432-A0304-12-0015-1
唑、苯并異
Figure 105130432-A0304-12-0015-1
唑、苯并噻唑、苯并異噻唑、苯并
Figure 105130432-A0304-12-0015-1
二唑、苯并噻二唑、糖精、吡咯啶及哌啶。 於該等中，較佳為吡咯、吡唑、咪唑、三唑、四唑、
Figure 105130432-A0304-12-0015-1
唑、異
Figure 105130432-A0304-12-0015-1
唑、噻唑、異噻唑、
Figure 105130432-A0304-12-0015-1
二唑、噻二唑、吲哚、吲唑、苯并咪唑、苯并三唑、苯并
Figure 105130432-A0304-12-0015-1
唑、苯并異
Figure 105130432-A0304-12-0015-1
唑、苯并噻唑、苯并異噻唑、苯并
Figure 105130432-A0304-12-0015-1
二唑、苯并噻二唑及糖精，更佳為咪唑、三唑、四唑、苯并三唑及吡唑。 亦可較佳地使用具有取代基之上述雜環化合物。 作為雜環化合物可具有之取代基，可列舉：碳原子數1～6之烷基、碳原子數3～8之環烷基、碳原子數1～6之烷氧基、碳原子數3～8之環烷氧基、碳原子數6～20之芳基、碳原子數7～20之芳烷基、碳原子數1～6之鹵化烷基、碳原子數2～7之脂肪族醯基、碳原子數2～7之鹵化脂肪族醯基、碳原子數7～20之芳基羰基、碳原子數2～7之羧基烷基、鹵素原子、羥基、巰基、碳原子數1～6之烷硫基、胺基、包含碳原子數1～6之烷基之單烷基胺基、包含碳原子數1～6之烷基之二烷基胺基、硝基及氰基等。 雜環化合物可於雜環上具有複數個取代基。於取代基之數量為複數個之情形時，複數個取代基可相同亦可不同。 於該等取代基包含脂肪族烴環或芳香族烴環等之情形時，該等環可進而具有與雜環化合物可具有之取代基相同之取代基。 作為取代基之烷基之碳原子數為1～6，較佳為1～4，更佳為1或2。碳原子數1～6之烷基之具體例可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基及正己基等。 於該等中，較佳為甲基及乙基，更佳為甲基。 作為取代基之環烷基之碳原子數為3～8，較佳為3～7，更佳為4～6。碳原子數3～8之環烷基之具體例為環丙基、環丁基、環戊基、環己基、環庚基及環辛基。 作為取代基之烷氧基之碳原子數為1～6，較佳為1～4，更佳為1或2。碳原子數1～6之烷氧基之具體例可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基及正己氧基等。 於該等中，較佳為甲氧基及乙氧基，更佳為甲氧基。 作為取代基之環烷氧基之碳原子數為3～8，較佳為3～7，更佳為4～6。碳原子數3～8之環烷氧基之具體例為環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基及環辛氧基。 作為取代基之芳基之碳原子數為6～20，較佳為6～12。作為碳原子數6～20之芳基之具體例，可列舉：苯基、α-萘基、β-萘基、聯苯-4-基、聯苯-3-基、聯苯-2-基、蒽-1-基、蒽-2-基、蒽-9-基、菲-1-基、菲-2-基、菲-3-基、菲-4-基及菲-9-基。於該等中，較佳為苯基、α-萘基、β-萘基、聯苯-4-基、聯苯-3-基及聯苯-2-基，更佳為苯基。 作為取代基之芳烷基之碳原子數為7～20，較佳為7～12。作為碳原子數7～20之芳烷基之具體例，可列舉：苄基、苯乙基、3-苯基-正丙基、4-苯基-正丁基、α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基及2-(β-萘基)乙基。於該等基中，較佳為苄基及苯乙基，更佳為苄基。 作為作為取代基之鹵化烷基中所包含之鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子。作為取代基之鹵化烷基之碳原子數為1～6，較佳為1～4，更佳為1或2。 碳原子數1～6之鹵化烷基之具體例為氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、1,1-二氟乙基、2,2,2-三氟乙基及五氟乙基。 作為取代基之脂肪族醯基之碳原子數為2～7，較佳為2～5，更佳為2或3。作為碳原子數2～7之脂肪族醯基之具體例，可列舉：乙醯基、丙醯基、丁醯基、戊醯基、己醯基及庚醯基。於該等中，較佳為乙醯基及丙醯基，更佳為乙醯基。 至於作為取代基之鹵化脂肪族醯基中所包含之鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子。作為取代基之鹵化脂肪族醯基之碳原子數為2～7，較佳為2～5，更佳為1或2。 碳原子數2～7之鹵化脂肪族醯基之具體例為氯乙醯基、二氯乙醯基、三氯乙醯基、氟乙醯基、二氟乙醯基、三氟乙醯基及五氟丙醯基。 作為取代基之芳基羰基之碳原子數為7～20，較佳為7～13。 碳原子數7～20之芳基羰基之具體例為苯甲醯基、α-萘甲醯基及β-萘甲醯基。 作為取代基之羧基烷基之碳原子數為2～7，較佳為2～5，更佳為2或3。作為碳原子數2～7之羧基烷基之具體例，可列舉：羧甲基、2-羧乙基、3-羧基-正丙基、4-羧基-正丁基、5-羧基-正戊基及6-羧基-正己基。於該等中，較佳為羧甲基。 作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。於該等中，較佳為氟原子、氯原子及溴原子，更佳為氯原子及溴原子。 作為取代基之烷硫基之碳原子數為1～6，較佳為1～4，更佳為1或2。碳原子數1～6之烷硫基之具體例可列舉：甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、第二丁硫基、第三丁硫基、正戊硫基及正己硫基等。 於該等中，較佳為甲硫基及乙硫基，更佳為甲硫基。 包含碳原子數1～6之烷基之單烷基胺基、及包含碳原子數1～6之烷基之二烷基胺基中所包含之烷基的具體例與上述作為取代基之烷基之具體例相同。 作為包含碳原子數1～6之烷基之單烷基胺基，較佳為乙基胺基及甲基胺基，更佳為甲基胺基。 作為包含碳原子數1～6之烷基之二烷基胺基，較佳為二乙基胺基及二甲基胺基，更佳為二甲基胺基。 作為雜環化合物之尤佳之具體例，可列舉下式之化合物。 [化9]
Figure 02_image017
表面處理劑中之雜環化合物之添加量係於不阻礙本發明之目的之範圍內並無特別限定。表面處理劑中之雜環化合物之添加量相對於上述矽烷基化劑1莫耳，較佳為0.1～20莫耳，更佳為0.2～10莫耳，最佳為0.5～5莫耳。 若雜環化合物之添加量為上述範圍內，則促進藉由表面處理劑進行之矽烷基化反應，容易提昇作為處理對象物之被處理體之表面之疏水性。 [溶劑] 表面處理劑可含有溶劑。藉由表面處理劑含有溶劑，容易進行藉由旋轉塗佈法或浸漬法等之被處理體之表面處理。其次，對表面處理劑中可含有之溶劑進行說明。 作為溶劑，只要為可溶解矽烷基化劑及雜環化合物，且對被處理體之表面(例如基板之表面(無機圖案、樹脂圖案等))之損害較少者，則可並無特別限定地使用先前公知之溶劑。 具體而言，可列舉：二甲基亞碸等亞碸類； 二甲基碸、二乙基碸、雙(2-羥基乙基)碸、四亞甲基碸等碸類； N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等醯胺類； N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-丙基-2-吡咯啶酮、N-羥基甲基-2-吡咯啶酮、N-羥基乙基-2-吡咯啶酮等內醯胺類； 1,3-二甲基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、1,3-二異丙基-2-咪唑啶酮等咪唑啶酮類； 二甲基乙二醇、二甲基二乙二醇、二甲基三乙二醇、甲基乙基二乙二醇、二乙二醇、三乙二醇丁基甲醚等二烷基乙二醇醚類； 乙二醇單甲醚、乙二醇單乙醚、乙二醇單-正丙醚、乙二醇單-正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單-正丙醚、二乙二醇單-正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單-正丙醚、丙二醇單-正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單-正丙醚、二丙二醇單-正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等(聚)伸烷基二醇單烷基醚類； 乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等(聚)伸烷基二醇單烷基醚乙酸酯類； 二甲醚、二乙醚、甲基乙醚、二丙醚、二異丙醚、二丁醚、二異戊醚、二乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙醚、四乙二醇二甲醚、四氫呋喃等其他醚類； 甲基乙基酮、環己酮、2-庚酮、3-庚酮等酮類； 2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷基酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基乙酸丁酯、3-甲基-3-甲氧基乙酸丁酯、3-甲基-3-甲氧基丙酸丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸正己酯、乙酸正庚酯、乙酸正辛酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、正辛酸甲酯、癸酸甲酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸乙酯、己二酸二甲酯、丙二醇二乙酸酯等其他酯類； β-丙內酯、γ-丁內酯、δ-戊內酯等內酯類； 正己烷、正戊烷、正辛烷、正壬烷、甲基辛烷、正癸烷、正十一烷、正十二烷、2,2,4,6,6-五甲基戊烷、2,2,4,4,6,8,8-七甲基壬烷、環己烷、甲基環己烷等直鏈狀、支鏈狀或環狀之脂肪族烴類； 苯、甲苯、二甲苯、1,3,5-三甲基苯、萘等芳香族烴類； 對薄荷烷、二苯基薄荷烷、檸檬烯、萜品烯、
Figure 105130432-A0304-02-0009-155
烷、降
Figure 105130432-A0304-02-0009-155
烷、蒎烷等萜烯類等。該等溶劑可單獨使用或混合2種以上而使用。 再者，於使用非極性之溶劑之情形時，有雜環化合物稍微難以溶解，於表面處理劑中包含雜環化合物之結晶之情形。 於因與藉由表面處理劑進行之表面處理之後續步驟之關係，必須於表面處理劑中使用非極性之溶劑之情形時，較佳為於進行藉由表面處理劑之表面處理後，視需要設置將析出之雜環化合物之結晶去除之步驟。 又，於本發明之表面處理劑之處理對象為樹脂圖案等有機材料之情形時，就可減輕對處理對象之損害之觀點而言，較佳地使用碳原子數為2至14之醚系溶劑，更佳地使用碳原子數為3至12之醚系溶劑。作為此種醚系溶劑，具體而言，可列舉：二甲醚、二乙醚、甲基乙醚、二丙醚、二異丙醚、二丁醚、二異戊醚等烷基醚。於該等中，較佳為二異丙醚、二丁醚及二異戊醚。上述醚系溶劑可單獨使用或組合2種以上而使用。 於使本發明之表面處理劑中含有溶劑之情形時，表面處理劑中所包含之矽烷基化劑與雜環化合物之合計之濃度實用上較佳為0.1質量%以上，更佳為0.1～30質量%，尤佳為0.5～20質量%，最佳為1～15質量%。 再者，關於以上所說明之表面處理劑，即便於與SUS(stainless steel，不鏽鋼)等金屬接觸之情形時，亦幾乎不會使金屬溶出。例如，即便使包含鐵之試片於室溫下浸漬於表面處理劑中5天以上，表面處理劑中之鐵之溶出亦為3 ppb以下。 ＜表面處理方法＞ 其次對本發明之表面處理方法進行說明。 本發明之表面處理方法係使上述本發明之表面處理劑暴露於被處理體之表面，對被處理體之表面進行處理者。 於被處理體為基板之情形時，如已說明般，作為本發明之表面處理方法中之處理對象之基板的表面除基板本身之表面以外，亦意指設置於基板上之無機圖案及樹脂圖案之表面、以及未圖案化之無機層及有機層之表面。對設置於基板上之無機圖案及樹脂圖案、以及未圖案化之無機層及有機層之表面之說明係如已描述般，故而省略此處之說明。 本發明之表面處理方法係對被處理體之表面進行矽烷基化處理者，該處理之目的可為任意者，作為該處理之目的之代表例，可列舉：(1)將基板等被處理體之表面進行疏水化，提昇對例如包含光阻劑等之樹脂圖案等之密接性；(2)於為基板之被處理體之表面之清洗中，防止基板之表面之無機圖案或樹脂圖案之圖案崩塌。 關於上述(1)，作為將上述本發明之表面處理劑暴露於被處理體之表面之方法，可並無特別限制地使用先前公知之方法，例如可列舉：使上述本發明之表面處理劑汽化而獲得蒸汽，使該蒸汽與被處理體之表面接觸之方法；藉由旋轉塗佈法或浸漬法等使上述本發明之表面處理劑與被處理體之表面接觸之方法等。 於作為光阻劑之膜之有機層之形成中所使用之基板為被處理體的情形時，較佳為表面處理劑之暴露於有機層之形成之前進行。 藉由此種操作，被處理體之表面進行矽烷基化，被處理體之表面之疏水性提昇。於被處理體為基板，且使用經表面處理劑處理之基板之情形時，基板表面進行疏水化，藉此例如提昇基板對光阻劑等之密接性。 關於上述(2)，於進行形成無機圖案或樹脂圖案後之清洗操作之前，對作為被處理體之基板之表面暴露上述本發明之表面處理劑即可。其次，對藉由實施此種表面處理，可於基板之表面之清洗中，防止基板之表面之無機圖案或樹脂圖案之圖案崩塌的原因進行說明。 通常，一般於在基板之表面形成無機圖案後，藉由SPM(硫酸/過氧化氫水)或APM(氨/過氧化氫水)等清洗液，清洗圖案之表面。又，一般亦於在基板之表面形成樹脂圖案後，藉由水或活性劑沖洗液等清洗液而清洗去除顯影殘渣或附著顯影液。 於本發明之表面處理方法中，於清洗此種無機圖案或樹脂圖案之前，藉由上述本發明之表面處理劑對圖案表面進行處理，將圖案之表面進行疏水化。 此處，於清洗時於無機圖案或樹脂圖案等圖案間發揮作用之力F係根據以下之式(I)之方式表示。其中，γ表示清洗液之表面張力，θ表示清洗液之接觸角，A表示圖案之縱橫比，D表示圖案側壁間之距離。 F＝2γ・cosθ・A/D・・・(I) 因此，若可將圖案之表面進行疏水化，提高清洗液之接觸角(使cosθ減小)，則可減小於後續之清洗時於圖案間發揮作用之力，可防止圖案崩塌。 該表面處理係藉由將形成有無機圖案或樹脂圖案之基板浸漬於表面處理劑中，或者對無機圖案或樹脂圖案塗佈或吹送表面處理劑而進行。處理時間較佳為1～60秒。又，較佳為於該表面處理後，圖案表面之水之接觸角成為40～120度，更佳為成為60～100度。 若以上之表面處理結束，則清洗無機圖案或樹脂圖案。於該清洗處理中，可直接採用先前於無機圖案或樹脂圖案之清洗處理中一直使用之清洗液。例如，針對無機圖案可列舉SPM或APM等，針對樹脂圖案可列舉水或活性劑沖洗液等。 再者，就產出量之方面而言，較佳為表面處理與清洗處理連續之處理。因此，作為表面處理劑，較佳為選擇與清洗液之置換性優異者。 關於本發明之表面處理方法中所使用之表面處理劑，如上述本發明之表面處理劑所述，含有矽烷基化劑、及不包含矽原子之含氮雜環化合物，該不包含矽原子之含氮雜環化合物係作為將被處理體之表面進行矽烷基化時之觸媒發揮作用的化合物。因此，藉由本發明之表面處理方法進行處理之被處理體之表面高度地疏水化(矽烷基化)。於被處理體為樹脂圖案或無機圖案之形成中所使用之基板之情形時，表面處理之結果為，提昇對樹脂圖案等之接著性，或防止圖案崩塌。 [實施例] 以下，藉由實施例更具體地說明本發明，但本發明並不限定於以下之實施例。 [實施例1～52及比較例1～8] 於實施例及比較例中，作為矽烷基化劑，使用以下之SA1～SA3、SA4：2,2,5,5-四甲基-2,5-二矽-1-氮雜環戊烷、SA5：2,2,4,4,6,6-六甲基環三矽氮烷。 [化10]
Figure 02_image019
於實施例及比較例中，作為不包含矽原子之含氮雜環化合物，使用以下之H1～H8。 [化11]
Figure 02_image021
於實施例及比較例中，作為溶劑，使用以下之S1～S15。 S1：丙二醇單甲醚乙酸酯 S2：乙酸正丁酯 S3：乙酸乙酯 S4：γ-丁內酯 S5：高沸點溶劑(三乙二醇丁基甲醚，沸點：261℃) S6：四乙二醇二甲醚 S7：二乙二醇二乙醚 S8：3-甲氧基乙酸丁酯 S9：3-甲基-3-甲氧基乙酸丁酯 S10：乙二醇單丁醚乙酸酯 S11：丙二醇二乙酸酯 S12：二乙二醇單乙醚乙酸酯 S12：己二酸二甲酯 S13：癸酸甲酯 S14：正辛酸甲酯 S15：乙酸正辛酯 分別均勻地混合表1～表3記載之種類及量(質量%)之矽烷基化劑、雜環化合物及溶劑，獲得各實施例及比較例之表面處理劑。 再者，於實施例15～19之表面處理劑中，產生雜環化合物之若干之溶化殘渣。 使用所獲得之表面處理劑，按照以下之方法，進行矽基板(Si)、矽熱氧化膜基板(thOx)、氮化矽基板(SiN)之表面處理，測定表面處理後之水之接觸角。將水之接觸角之測定結果記載於表1～表3。 水之接觸角之測定係使用Dropmaster700(協和界面科學股份有限公司製造)，對經表面處理之基板之表面滴加純水液滴(1.8 μL)，以滴加10秒後之接觸角之形式進行測定。 ＜表面處理方法＞ 首先，於25℃下使基板浸漬於濃度1質量%之HF(hydrofluoric acid，氫氟酸)水溶液中1分鐘。浸漬後，藉由離子交換蒸餾水將基板清洗1分鐘。藉由氮氣流使水洗後之基板乾燥。 於25℃下使乾燥後之基板浸漬於各實施例及比較例之表面處理劑中60秒，進行基板之表面處理。利用異丙醇將表面處理後之基板清洗1分鐘後，進行藉由離子交換蒸餾水之清洗1分鐘。藉由氮氣流使清洗後之基板乾燥，獲得經表面處理之基板。 [表1]
Figure 105130432-A0304-0001
 [表2]
Figure 105130432-A0304-0002
 [表3]
Figure 105130432-A0304-0003
 根據比較例1與實施例1～3之比較、比較例2與實施例4～6之比較、比較例3與實施例5～9之比較、比較例7與實施例22之比較、及比較例8與實施例23之比較可知，表面處理劑含有矽烷基化劑、以及不包含矽原子之含氮雜環化合物，藉此表面處理時之藉由矽烷基化劑之疏水化之效率明顯提昇。 根據比較例1與比較例4及5之比較可知，即便使表面處理劑中含有含氮雜環化合物作為包含矽原子之矽烷基化劑，表面處理時之藉由矽烷基化劑之疏水化之效率亦並未大幅提昇。 根據實施例6與實施例10～13及實施例24～33之比較可知，關於含有矽烷基化劑、以及不包含矽原子之含氮雜環化合物之表面處理劑，不論溶劑之種類，均可獲得良好之表面處理效果。 根據實施例6與實施例14～21及實施例34～52之比較可知，使用各種化合物作為雜環化合物，可獲得與表面處理時之藉由矽烷基化劑之疏水化之效率之提昇相關之所需的效果。 尤其根據實施例15～19、34、37、39及41～50可知，即便於雜環化合物之含量稍微較少之情形時，藉由表面處理劑獲得之良好之疏水化之效果亦不會大幅受損。<Surface treatment agent> The surface treatment agent will be described. The surface treatment agent is used when the surface of the object to be treated is silylated. The type of the object to be processed is not particularly limited. The object to be processed is preferably a "substrate". Here, as the "substrate" to be the target of the silylation treatment, a substrate used for manufacturing a semiconductor device can be exemplified, and the "surface of the substrate" can also exemplify in addition to the surface of the substrate itself: an inorganic pattern provided on the substrate And the surface of the resin pattern; and the surface of the unpatterned inorganic layer and organic layer. As the inorganic pattern provided on the substrate, a pattern formed by forming an etching mask on the surface of the inorganic layer existing on the substrate by using a photoresist method, and then performing an etching treatment, can be exemplified. As the inorganic layer, in addition to the substrate itself, an oxide film of an element constituting the substrate; a film or layer of inorganic substances such as silicon nitride, titanium nitride, and tungsten formed on the surface of the substrate can also be exemplified. It does not specifically limit as such a film or layer, The film or layer of an inorganic substance formed in the manufacturing process of a semiconductor device, etc. can be illustrated. As the resin pattern provided on the substrate, a resin pattern formed on the substrate by a photoresist method can be exemplified. Such a resin pattern is formed, for example, by forming an organic layer as a photoresist film on a substrate, and exposing and developing the organic layer through a photomask. As the organic layer, in addition to the surface of the substrate itself, the surface of a laminated film provided on the surface of the substrate can also be exemplified. The organic layer is not particularly limited, and it can be exemplified as an organic film provided in order to form an etching mask during the manufacturing process of a semiconductor device. Surface treatment can be performed by applying a solvent-added solution-type surface treatment agent to the surface of a substrate or the like by a method such as a spin coating method or a dipping method. The surface treatment agent of the present invention includes a silylation agent and a nitrogen-containing heterocyclic compound (hereinafter, also referred to as a heterocyclic compound) that does not include a silicon atom. Hereinafter, each component will be described. [Silylation Agent] First, the silylation agent used in the surface treatment agent of the present invention will be described. The silylation agent used in the surface treatment agent of the present invention is a component used to silylate the surface of the object to be treated to make the surface of the object to be treated more hydrophobic. The silylating agent contained in the surface treatment agent of the present invention is not particularly limited, and all previously known silylating agents can be used. As such a silylating agent, for example, a silylating agent or a cyclic silazane compound having a substituent represented by the following general formula (2) can be used. [化1]
Figure 02_image001
(In the above general formula (2), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and the total of the carbon atoms contained in R 4 , R 5 and R 6 The number is 1 or more) As the silylating agent having the substituent represented by the above general formula (2), more specifically, the silyl group represented by the following general formulas (3) to (8) can be used化剂。 Chemical agent. [化2]
Figure 02_image003
(In the above general formula (3), R 4 , R 5 and R 6 are the same as the above general formula (2), R 7 represents a hydrogen atom, or a saturated or unsaturated alkyl group, and R 8 represents a hydrogen atom, saturated or unsaturated Saturated alkyl, saturated or unsaturated cycloalkyl, acetyl, or saturated or unsaturated heterocycloalkyl. R 7 and R 8 may be bonded to each other to form a ring structure containing a nitrogen atom) [Chemical Formula 3]
Figure 02_image005
(In the above general formula (4), R 4 , R 5 and R 6 are the same as the above general formula (2), R 9 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, and R 10 , R 11 and R 12 each independently represent a hydrogen atom or an organic group, and the total number of carbon atoms contained in R 10 , R 11 and R 12 is 1 or more) [Chemical 4]
Figure 02_image007
(In the above general formula (5), R 4 , R 5 and R 6 are the same as the above general formula (2), X represents O, CHR 14 , CHOR 14 , CR 14 R 14 or NR 15 , R 13 and R 14 Each independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trialkylsilyl group, a trialkylsilyloxy group, an alkoxy group, a phenyl group, a phenylethyl group or an acetyl group , R 15 represents a hydrogen atom, an alkyl group or a trialkylsilyl group) [化5]
Figure 02_image009
(In the above general formula (6), R 4 , R 5 and R 6 are the same as the above general formula (2), R 9 is the same as the above general formula (4), R 16 represents a hydrogen atom, saturated or unsaturated alkane Group, trifluoromethyl or trialkylsilylamino group) [Chemical 6]
Figure 02_image011
(In the above general formula (7), R 17 and R 18 each independently represent a hydrogen atom, an alkyl group, and a trialkylsilyl group, and at least one of R 17 and R 18 represents a trialkylsilyl group) [Chemical Formula 7 ]
Figure 02_image013
(In the above general formula (8), R 19 represents a trialkylsilyl group, and R 20 and R 21 each independently represent a hydrogen atom or an organic group) [Chemical Formula 8]
Figure 02_image015
(In the above general formula (9), R 4 , R 5 and R 6 are the same as the above general formula (2), R 22 represents an organic group, R 23 does not exist, or when it exists, represents -SiR 24 R 25 R 26. R 24 , R 25 and R 26 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and any one of R 24 , R 25 and R 26 can be connected to R 4 , Any one of R 5 and R 6 is bonded to form an imino group) As the silylating agent represented by the above formula (3), N,N-dimethylaminotrimethylsilane, N,N-Dimethylaminodimethylsilane, N,N-Dimethylaminomonomethylsilane, N,N-Diethylaminotrimethylsilane, tertiary butylaminotrimethyl Silane, Allylaminotrimethylsilane, Trimethylsilylacetamide, N,N-Dimethylaminodimethylvinylsilane, N,N-Dimethylaminodimethyl Propylsilane, N,N-dimethylaminodimethyloctylsilane, N,N-dimethylaminodimethylphenylethylsilane, N,N-dimethylaminodimethyl Phenylsilane, N,N-dimethylaminodimethyl-tert-butylsilane, N,N-dimethylaminotriethylsilane, trimethylsilanamine, monomethylsilylimidazole, Dimethylsilyl imidazole, trimethylsilyl imidazole, monomethylsilyl triazole, dimethylsilyl triazole, trimethylsilyl triazole, etc. Examples of the silylation agent represented by the above formula (4) include: hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane Nitrogen, 1,3-dimethyldisilazane, 1,2-di-N-octyltetramethyldisilazane, 1,2-divinyltetramethyldisilazane, heptamethyl Disilazane, nonamethyltrisilazane, tris(dimethylsilyl)amine, tris(trimethylsilyl)amine, pentamethylethyldisilazane, pentamethylvinyldi Silazane, pentamethyl propyl disilazane, pentamethyl phenyl ethyl disilazane, pentamethyl-tertiary butyl disilazane, pentamethyl phenyl disilazane, three Methyl triethyl disilazane, etc. Examples of the silylating agent represented by the above formula (5) include: trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl propionate, trimethylbutyrate Silyl ester, trimethylsilyloxy-3-penten-2-one, etc. As the silylating agent represented by the above formula (6), bis(trimethylsilyl)urea, N-trimethylsilylacetamide, N-methyl-N-trimethylsilyl Trifluoroacetamide and so on. Examples of the compound represented by the above formula (7) include bis(trimethylsilyl)trifluoroacetamide and the like, and examples of the compound represented by the above formula (8) include: 2-trimethylsilanoxy Base pent-2-en-4-one and so on. Examples of the compound represented by the above formula (9) include 1,2-bis(dimethylchlorosilyl)ethane, tert-butyldimethylchlorosilane, and the like. Examples of the cyclic silazane compound include: 2,2,5,5-tetramethyl-2,5-disilil-1-azacyclopentane, 2,2,6,6-tetramethyl- Cyclic disilazane compounds such as 2,6-disilaza-1-azacyclohexane; 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6- Cyclic trisilazane compounds such as trimethyl-2,4,6-trivinylcyclotrisilazane; 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane Cyclic tetrasilazane compounds such as alkanes. Here, if attention is paid to a substituent bonded to a silicon atom, it is preferable to use a silylation agent in which a so-called bulky substituent having a larger number of carbon atoms contained in the substituent is bonded to the silicon atom. When the surface treatment agent contains such a silylation agent, the surface of the treated body treated by the surface treatment agent can be made more hydrophobic. When the processed object is a substrate, the adhesion between the surface of the processed substrate and the resin pattern can be improved by this. In addition, as explained below, the hydrophobicity of the surface of the substrate to be processed, especially the surface of the inorganic pattern or the resin pattern, becomes greater, thereby preventing the pattern of the inorganic pattern or the resin pattern from collapsing. Therefore, it is preferable that the total number of carbon atoms contained in R 4 , R 5 and R 6 in the above general formula (2) is 3 or more. Among them, from the viewpoint of obtaining sufficient reactivity in the silylation reaction, it is more preferable that in the above general formula (2), any one of R 4 , R 5 and R 6 has 2 carbon atoms The above organic groups (hereinafter, referred to as "specific organic groups" in this paragraph), and the remaining two are independently methyl or ethyl. Examples of the specific organic group include: branched and/or optionally substituted alkyl group having 2 to 20 carbon atoms; optionally substituted vinyl group; optionally substituted aryl group. The number of carbon atoms of the specific organic group is more preferably 2-12, still more preferably 2-10, and particularly preferably 2-8. From this point of view, among the silylating agents exemplified above, N,N-dimethylaminodimethylvinylsilane, N,N-dimethylaminodimethyl Propyl silane, N,N-dimethylamino dimethyl octyl silane, N,N-dimethylamino dimethyl phenyl ethyl silane, N,N-dimethylamino dimethyl N,N-dimethylaminodimethyl-tertiary butylsilane, N,N-dimethylaminotriethylsilane, N,N-dimethylaminotrimethyl Silane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylphenylethyldisilazane, pentamethyl-third Butyl disilazane, pentamethyl phenyl disilazane, trimethyl triethyl disilazane, etc. The silylating agents exemplified above can be used alone or in combination of two or more kinds. [Heterocyclic compound] The surface treatment agent contains a nitrogen-containing heterocyclic compound (also referred to simply as a heterocyclic compound) that does not contain a silicon atom. So far, the silylation of the surface of substrates and other objects to be processed has the following situations: for example, when hexamethyldisilazane (HMDS) is used as the silylation agent, the reactivity of the silylation agent is insufficient. Therefore, the silylation reaction requires more time, or sufficient hydrophobicity of the surface of the treated body cannot be obtained. However, when the surface treatment agent contains a silylation agent and a nitrogen-containing heterocyclic compound that does not contain silicon atoms, the silylation reaction using the silylation agent is promoted by the catalytic action of the nitrogen-containing heterocyclic compound , The surface of the treated body is highly hydrophobic. Therefore, if the surface treatment agent of the present invention is used for the silylation treatment of the surface of the object to be treated, the surface of the object to be treated can be highly hydrophobicized. In addition, if the surface treatment agent of the present invention is used to hydrophobize the surface of the object to be treated to the same degree as before, the time required for the surface treatment can be shortened. The heterocyclic compound is not particularly limited as long as it does not contain a silicon atom and contains a nitrogen atom in the ring structure. The heterocyclic compound may contain heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms in the ring. The heterocyclic compound is preferably a compound containing a nitrogen-containing heterocyclic ring having aromaticity. Since the heterocyclic compound contains an aromatic nitrogen-containing heterocyclic ring, the hydrophobicity of the surface of the treated object treated with the surface treatment agent can be increased. The heterocyclic compound may be a compound in which two or more plural rings are bonded via a single bond or a multivalent linking group with more than two valence. In this case, the two or more plural rings bonded by the linking group may include at least one nitrogen-containing heterocyclic ring. Among the multivalent linking groups, the divalent linking group is preferable in terms of the small steric hindrance between the rings. Specific examples of the divalent linking group include: alkylene groups having 1 to 6 carbon atoms, -CO-, -CS-, -O-, -S-, -NH-, -N=N-,- CO-O-, -CO-NH-, -CO-S-, -CS-O-, -CS-S-, -CO-NH-CO-, -NH-CO-NH-, -SO- and- SO 2 -etc. In terms of easy preparation of a uniform surface treatment agent, the number of rings contained in a compound formed by bonding two or more plural rings through a multivalent linking group is preferably 4 or less, more preferably 3 Below, the best is 2. Furthermore, for example, regarding condensed rings such as a naphthalene ring, the number of rings is set to two. The heterocyclic compound may also be a nitrogen-containing heterocyclic compound formed by the condensation of two or more plural rings. In this case, at least one of the rings constituting the condensed ring may be a nitrogen-containing heterocyclic ring. In terms of easy preparation of a uniform surface treatment agent, the number of rings contained in a nitrogen-containing heterocyclic compound formed by condensation of two or more plural rings is preferably 4 or less, preferably 3 or less, most Best is 2. As far as the effect of the surface treatment using the surface treatment agent is relatively good, the heterocyclic compound is preferably a condensed polycyclic ring containing a nitrogen-containing 5-membered ring or a nitrogen-containing 5-membered ring skeleton. As preferred examples of heterocyclic compounds, for example, pyridine,
Figure 105130432-A0304-12-0020-4
Pyridine
Figure 105130432-A0304-12-0020-4
, Pyrimidine, three
Figure 105130432-A0304-12-0020-4
,four
Figure 105130432-A0304-12-0020-4
, Pyrrole, pyrazole, imidazole, triazole, tetrazole,
Figure 105130432-A0304-12-0015-1
Azole, iso
Figure 105130432-A0304-12-0015-1
Azole, thiazole, isothiazole,
Figure 105130432-A0304-12-0015-1
Diazole, thiadiazole, quinoline, isoquinoline,
Figure 105130432-A0304-12-xxxx-6
Phylline, Phthalo
Figure 105130432-A0304-12-0020-4
Quine
Figure 105130432-A0304-12-0015-1
Morpholine, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzo
Figure 105130432-A0304-12-0015-1
Azole, benziso
Figure 105130432-A0304-12-0015-1
Azole, benzothiazole, benzisothiazole, benzo
Figure 105130432-A0304-12-0015-1
Diazole, benzothiadiazole, saccharin, pyrrolidine and piperidine. Among them, pyrrole, pyrazole, imidazole, triazole, tetrazole,
Figure 105130432-A0304-12-0015-1
Azole, iso
Figure 105130432-A0304-12-0015-1
Azole, thiazole, isothiazole,
Figure 105130432-A0304-12-0015-1
Diazole, thiadiazole, indole, indazole, benzimidazole, benzotriazole, benzo
Figure 105130432-A0304-12-0015-1
Azole, benziso
Figure 105130432-A0304-12-0015-1
Azole, benzothiazole, benzisothiazole, benzo
Figure 105130432-A0304-12-0015-1
Diazole, benzothiadiazole and saccharin, more preferably imidazole, triazole, tetrazole, benzotriazole and pyrazole. The aforementioned heterocyclic compounds having substituents can also be preferably used. Examples of substituents that the heterocyclic compound may have include: alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and 3 to 6 carbon atoms. Cycloalkoxy of 8, aryl group of 6 to 20 carbon atoms, aralkyl group of 7 to 20 carbon atoms, halogenated alkyl group of 1 to 6 carbon atoms, aliphatic acyl group of 2 to 7 carbon atoms , Halogenated aliphatic acyl groups with 2 to 7 carbon atoms, arylcarbonyl groups with 7 to 20 carbon atoms, carboxyalkyl groups with 2 to 7 carbon atoms, halogen atoms, hydroxyl groups, mercapto groups, and ones with 1 to 6 carbon atoms Alkylthio groups, amino groups, monoalkylamino groups including alkyl groups having 1 to 6 carbon atoms, dialkylamino groups including alkyl groups having 1 to 6 carbon atoms, nitro groups, cyano groups, and the like. The heterocyclic compound may have multiple substituents on the heterocyclic ring. When the number of substituents is plural, the plural substituents may be the same or different. When the substituents include an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, etc., the rings may further have the same substituents as the substituents that the heterocyclic compound may have. The number of carbon atoms of the alkyl group as the substituent is 1 to 6, preferably 1 to 4, and more preferably 1 or 2. Specific examples of alkyl groups having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl And n-hexyl and so on. Among them, methyl and ethyl are preferred, and methyl is more preferred. The number of carbon atoms of the cycloalkyl group as a substituent is 3-8, preferably 3-7, more preferably 4-6. Specific examples of the cycloalkyl group having 3 to 8 carbon atoms are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The number of carbon atoms of the alkoxy group as the substituent is 1 to 6, preferably 1 to 4, more preferably 1 or 2. Specific examples of alkoxy groups having 1 to 6 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, The tertiary butoxy group, n-pentoxy group and n-hexoxy group. Among them, methoxy and ethoxy are preferred, and methoxy is more preferred. The number of carbon atoms of the cycloalkoxy group as a substituent is 3-8, preferably 3-7, more preferably 4-6. Specific examples of the cycloalkoxy group having 3 to 8 carbon atoms are cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy. The number of carbon atoms of the aryl group as a substituent is 6-20, preferably 6-12. Specific examples of aryl groups having 6 to 20 carbon atoms include: phenyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, and biphenyl-2-yl , Anthracene-1-yl, anthracene-2-yl, anthracene-9-yl, phenanthrene-1-yl, phenanthrene-2-yl, phenanthrene-3-yl, phenanthrene-4-yl and phenanthrene-9-yl. Among them, phenyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl and biphenyl-2-yl are preferred, and phenyl is more preferred. The number of carbon atoms of the aralkyl group as the substituent is 7-20, preferably 7-12. Specific examples of aralkyl groups having 7 to 20 carbon atoms include benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl and 2-(β-naphthyl)ethyl. Among these groups, benzyl and phenethyl are preferred, and benzyl is more preferred. The halogen atom contained in the halogenated alkyl group as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of carbon atoms of the halogenated alkyl group as the substituent is 1 to 6, preferably 1 to 4, and more preferably 1 or 2. Specific examples of halogenated alkyl groups having 1 to 6 carbon atoms are chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl , 2,2,2-Trifluoroethyl and pentafluoroethyl. The number of carbon atoms of the aliphatic acyl group as a substituent is 2-7, preferably 2-5, more preferably 2 or 3. Specific examples of the aliphatic aliphatic group having 2 to 7 carbon atoms include acetyl, propionyl, butyryl, pentanyl, hexyl, and heptyl. Among them, acetyl and propyl are preferred, and acetyl is more preferred. As for the halogen atom contained in the halogenated aliphatic acyl group as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. The number of carbon atoms of the halogenated aliphatic acyl group as a substituent is 2-7, preferably 2-5, more preferably 1 or 2. Specific examples of halogenated aliphatic acyl groups having 2 to 7 carbon atoms are chloroacetinyl, dichloroacetinyl, trichloroacetinyl, fluoroacetinyl, difluoroacetinyl, trifluoroacetinyl and Pentafluoropropionyl. The number of carbon atoms of the arylcarbonyl group as a substituent is 7-20, preferably 7-13. Specific examples of the arylcarbonyl group having 7 to 20 carbon atoms are benzyl, α-naphthyl and β-naphthyl. The number of carbon atoms of the carboxyalkyl group as a substituent is 2-7, preferably 2-5, more preferably 2 or 3. Specific examples of carboxyalkyl groups having 2 to 7 carbon atoms include: carboxymethyl, 2-carboxyethyl, 3-carboxy-n-propyl, 4-carboxy-n-butyl, 5-carboxy-n-pentyl Group and 6-carboxy-n-hexyl. Among them, carboxymethyl is preferred. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a chlorine atom and a bromine atom are more preferable. The alkylthio group as the substituent has 1 to 6, preferably 1 to 4, and more preferably 1 or 2. Specific examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, second butylthio, The third butylthio, n-pentylthio and n-hexylthio, etc. Among them, methylthio and ethylthio are preferred, and methylthio is more preferred. Specific examples of the alkyl group contained in the monoalkylamino group containing an alkyl group having 1 to 6 carbon atoms and the dialkylamino group containing an alkyl group having 1 to 6 carbon atoms are the same as the above-mentioned substituents The specific examples of the base are the same. The monoalkylamino group containing an alkyl group having 1 to 6 carbon atoms is preferably an ethylamino group and a methylamino group, and more preferably a methylamino group. The dialkylamino group containing an alkyl group having 1 to 6 carbon atoms is preferably a diethylamino group and a dimethylamino group, and more preferably a dimethylamino group. As a particularly preferable specific example of the heterocyclic compound, a compound of the following formula can be cited. [化9]
Figure 02_image017
The addition amount of the heterocyclic compound in the surface treatment agent is not particularly limited within a range that does not hinder the purpose of the present invention. The addition amount of the heterocyclic compound in the surface treatment agent is preferably 0.1-20 mol, more preferably 0.2-10 mol, and most preferably 0.5-5 mol relative to 1 mol of the above-mentioned silylating agent. If the addition amount of the heterocyclic compound is within the above range, the silylation reaction by the surface treatment agent is promoted, and the hydrophobicity of the surface of the object to be treated is easily improved. [Solvent] The surface treatment agent may contain a solvent. Since the surface treatment agent contains a solvent, it is easy to perform surface treatment of the object to be treated by spin coating or dipping. Next, the solvent that can be contained in the surface treatment agent will be described. The solvent is not particularly limited as long as it can dissolve the silylating agent and heterocyclic compound and has less damage to the surface of the object to be processed (for example, the surface of the substrate (inorganic pattern, resin pattern, etc.)) Use previously known solvents. Specifically, it can be exemplified: sulfites such as dimethyl sulfite; sulfites such as dimethyl sulfite, diethyl sulfite, bis(2-hydroxyethyl) sulfite, and tetramethylene sulfite; N,N- Dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide and other amides; N -Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl- Endoamines such as 2-pyrrolidone; 1,3-dimethyl-2-imidazolidone, 1,3-diethyl-2-imidazolidone, 1,3-diisopropyl-2- Imidazolidinones such as imidazolidinone; dimethyl glycol, dimethyl diethylene glycol, dimethyl triethylene glycol, methyl ethyl diethylene glycol, diethylene glycol, triethylene glycol Dialkyl glycol ethers such as butyl methyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, three Propylene glycol monoethyl ether and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene two Alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; Methyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether , Tetraethylene glycol dimethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; methyl 2-hydroxypropionate, 2-hydroxypropyl Alkyl lactate such as ethyl ester; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, butyl 3-methoxyacetate, 3-methyl Butyl-3-methoxyacetate, butyl 3-methyl-3-methoxypropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, N-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Ester, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, 2-side oxygen Ethyl butyrate, dimethyl adipate, propylene glycol diacetate and other esters; β-propiolactone, γ-butyrolactone, δ-valerolactone and other lactones; n-hexane, n-hexane Pentane, n-octane, n-nonane, methyl octane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylpentane, 2,2, 4,4,6,8,8-Heptamethylnonane, cyclohexane, methylcyclohexane and other linear, branched or cyclic aliphatic hydrocarbons; benzene, toluene, xylene, 1 ,3,5-Trimethylbenzene, naphthalene and other aromatic hydrocarbons; p-menthane, diphenyl menthane, limonene, terpinene,
Figure 105130432-A0304-02-0009-155
Alkane, drop
Figure 105130432-A0304-02-0009-155
Terpenes such as alkanes and pinanes. These solvents can be used individually or in mixture of 2 or more types. Furthermore, when a non-polar solvent is used, the heterocyclic compound is slightly difficult to dissolve, and the surface treatment agent contains the crystal of the heterocyclic compound. When it is necessary to use a non-polar solvent in the surface treatment agent due to the relationship with the subsequent steps of the surface treatment by the surface treatment agent, it is preferable to perform the surface treatment by the surface treatment agent, if necessary Set up a step to remove the crystals of the precipitated heterocyclic compound. In addition, when the surface treatment agent of the present invention is an organic material such as a resin pattern, it is preferable to use an ether solvent with 2 to 14 carbon atoms from the viewpoint of reducing damage to the treatment target , It is more preferable to use ether solvents with 3 to 12 carbon atoms. Specific examples of such ether-based solvents include alkyl ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, and diisoamyl ether. Among them, diisopropyl ether, dibutyl ether and diisoamyl ether are preferred. The above-mentioned ether-based solvents can be used alone or in combination of two or more kinds. When the surface treatment agent of the present invention contains a solvent, the total concentration of the silylating agent and the heterocyclic compound contained in the surface treatment agent is practically preferably 0.1% by mass or more, more preferably 0.1-30 The mass% is preferably 0.5-20% by mass, most preferably 1-15% by mass. Furthermore, regarding the surface treatment agent described above, even when it comes into contact with metals such as SUS (stainless steel, stainless steel), it hardly causes the metal to elute. For example, even if a test piece containing iron is immersed in a surface treatment agent at room temperature for more than 5 days, the elution of iron in the surface treatment agent is 3 ppb or less. <Surface Treatment Method> Next, the surface treatment method of the present invention will be described. The surface treatment method of the present invention exposes the surface treatment agent of the present invention to the surface of the object to be treated and treats the surface of the object to be treated. When the object to be processed is a substrate, as already explained, the surface of the substrate to be processed in the surface treatment method of the present invention, in addition to the surface of the substrate itself, also means the inorganic pattern and resin pattern provided on the substrate The surface, and the surface of the unpatterned inorganic layer and organic layer. The description of the inorganic pattern and resin pattern, and the surface of the unpatterned inorganic layer and organic layer provided on the substrate are as already described, so the description here is omitted. The surface treatment method of the present invention is one that performs silylation treatment on the surface of the object to be treated, and the purpose of the treatment can be any one. As a representative example of the purpose of the treatment, there can be cited: (1) The treatment of a substrate such as a substrate The surface of the substrate is hydrophobized to improve the adhesion to the resin pattern containing photoresist, etc.; (2) In the cleaning of the surface of the substrate to be processed, prevent the inorganic pattern or the pattern of the resin pattern on the surface of the substrate collapse. Regarding the above (1), as a method for exposing the surface treatment agent of the present invention to the surface of the object to be treated, a previously known method can be used without particular limitation, for example: vaporizing the surface treatment agent of the present invention A method of obtaining steam and contacting the steam with the surface of the object to be processed; a method of contacting the surface treatment agent of the present invention with the surface of the object to be processed by spin coating or dipping. When the substrate used in the formation of the organic layer of the photoresist film is the object to be processed, it is preferably performed before the surface treatment agent is exposed to the formation of the organic layer. By this operation, the surface of the processed body is silylated, and the hydrophobicity of the surface of the processed body is improved. When the object to be processed is a substrate and a substrate treated with a surface treatment agent is used, the surface of the substrate is hydrophobicized, for example, to improve the adhesion of the substrate to the photoresist. Regarding the above (2), before performing the cleaning operation after forming the inorganic pattern or the resin pattern, the surface treatment agent of the present invention may be exposed to the surface of the substrate as the object to be processed. Next, the reason why the inorganic pattern or resin pattern on the surface of the substrate can be prevented from collapsing during the cleaning of the surface of the substrate by performing such surface treatment will be described. Generally, after the inorganic pattern is formed on the surface of the substrate, the surface of the pattern is cleaned with a cleaning solution such as SPM (sulfuric acid/hydrogen peroxide water) or APM (ammonia/hydrogen peroxide water). In addition, generally, after the resin pattern is formed on the surface of the substrate, it is cleaned and removed with a cleaning solution such as water or an active agent rinse solution to remove the development residue or the attached developer. In the surface treatment method of the present invention, before cleaning the inorganic pattern or resin pattern, the surface of the pattern is treated with the surface treatment agent of the present invention to make the surface of the pattern hydrophobic. Here, the force F that acts between patterns such as an inorganic pattern or a resin pattern during cleaning is represented by the following formula (I). Among them, γ represents the surface tension of the cleaning solution, θ represents the contact angle of the cleaning solution, A represents the aspect ratio of the pattern, and D represents the distance between the side walls of the pattern. F=2γ・cosθ・A/D・・・(I) Therefore, if the surface of the pattern can be hydrophobicized to increase the contact angle of the cleaning solution (reduce the cosθ), it can be reduced during subsequent cleaning. The force exerted between patterns can prevent patterns from collapsing. The surface treatment is performed by immersing a substrate on which an inorganic pattern or a resin pattern is formed in a surface treatment agent, or applying or blowing the surface treatment agent on the inorganic pattern or the resin pattern. The treatment time is preferably 1 to 60 seconds. Furthermore, after the surface treatment, it is preferable that the contact angle of water on the surface of the pattern is 40 to 120 degrees, more preferably 60 to 100 degrees. After the above surface treatment is completed, the inorganic pattern or resin pattern is cleaned. In the cleaning process, the cleaning solution that has been used in the cleaning process of inorganic patterns or resin patterns can be directly used. For example, for the inorganic pattern, SPM or APM may be mentioned, and for the resin pattern, water or an active agent rinse may be mentioned. Furthermore, in terms of throughput, it is preferable to perform continuous surface treatment and cleaning treatment. Therefore, as the surface treatment agent, it is preferable to select one that is excellent in replacement with the cleaning solution. Regarding the surface treatment agent used in the surface treatment method of the present invention, as described in the above-mentioned surface treatment agent of the present invention, a nitrogen-containing heterocyclic compound containing a silylating agent and a silicon atom is contained, which does not contain a silicon atom The nitrogen-containing heterocyclic compound is a compound that functions as a catalyst when the surface of the object to be treated is silylated. Therefore, the surface of the object treated by the surface treatment method of the present invention is highly hydrophobized (silylated). When the object to be processed is a substrate used in the formation of a resin pattern or an inorganic pattern, the result of the surface treatment is to improve the adhesion to the resin pattern or the like, or to prevent the pattern from collapsing. [Examples] Hereinafter, the present invention will be explained more specifically through examples, but the present invention is not limited to the following examples. [Examples 1 to 52 and Comparative Examples 1 to 8] In the Examples and Comparative Examples, the following SA1 to SA3 and SA4 were used as the silylating agent: 2,2,5,5-tetramethyl-2, 5-Disilil-1-azacyclopentane, SA5: 2,2,4,4,6,6-hexamethylcyclotrisilazane. [化10]
Figure 02_image019
In the Examples and Comparative Examples, the following H1 to H8 are used as nitrogen-containing heterocyclic compounds not containing silicon atoms. [化11]
Figure 02_image021
In the examples and comparative examples, the following S1 to S15 were used as the solvent. S1: Propylene glycol monomethyl ether acetate S2: n-butyl acetate S3: ethyl acetate S4: γ-butyrolactone S5: high boiling point solvent (triethylene glycol butyl methyl ether, boiling point: 261°C) S6: tetraethylenedi Alcohol dimethyl ether S7: Diethylene glycol diethyl ether S8: 3-methoxybutyl acetate S9: 3-methyl-3-methoxybutyl acetate S10: Ethylene glycol monobutyl ether acetate S11: Propylene glycol diacetate S12: Diethylene glycol monoethyl ether acetate S12: Dimethyl adipate S13: Methyl decanoate S14: Methyl n-octanoate S15: N-octyl acetate were mixed uniformly Table 1 ~ Table 3 The type and amount (mass%) of the silylation agent, heterocyclic compound, and solvent described in 3 were used to obtain the surface treatment agents of the respective Examples and Comparative Examples. Furthermore, in the surface treatment agents of Examples 15-19, some melting residues of heterocyclic compounds were generated. Using the obtained surface treatment agent, the surface treatment of silicon substrate (Si), silicon thermal oxide film substrate (thOx), and silicon nitride substrate (SiN) was performed according to the following method, and the contact angle of water after the surface treatment was measured. The measurement results of the contact angle of water are described in Tables 1 to 3. The contact angle of water was measured using Dropmaster700 (manufactured by Concord Interface Science Co., Ltd.), and pure water droplets (1.8 μL) were added to the surface of the surface-treated substrate, and the contact angle was measured after 10 seconds. Determination. <Surface treatment method> First, the substrate is immersed in an HF (hydrofluoric acid) aqueous solution with a concentration of 1% by mass at 25°C for 1 minute. After immersion, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate after washing with water is dried by nitrogen flow. The dried substrate was immersed in the surface treatment agent of each example and comparative example at 25°C for 60 seconds to perform surface treatment of the substrate. After cleaning the surface-treated substrate with isopropanol for 1 minute, cleaning with ion-exchanged distilled water is performed for 1 minute. The cleaned substrate is dried by a nitrogen stream to obtain a surface-treated substrate. [Table 1]
Figure 105130432-A0304-0001
 [Table 2]
Figure 105130432-A0304-0002
 [table 3]
Figure 105130432-A0304-0003
 According to the comparison between Comparative Example 1 and Examples 1 to 3, Comparative Example 2 and Examples 4-6, Comparative Example 3 and Examples 5-9, Comparative Example 7 and Example 22, and Comparative Examples The comparison between 8 and Example 23 shows that the surface treatment agent contains a silylation agent and a nitrogen-containing heterocyclic compound that does not contain silicon atoms, so that the efficiency of hydrophobization by the silylation agent during surface treatment is significantly improved. According to the comparison between Comparative Example 1 and Comparative Examples 4 and 5, even if the surface treatment agent contains a nitrogen-containing heterocyclic compound as a silicon atom-containing silylation agent, the surface treatment is hydrophobized by the silylation agent Efficiency has not improved significantly. According to the comparison of Example 6 with Examples 10-13 and Examples 24-33, the surface treatment agent containing the silylating agent and the nitrogen-containing heterocyclic compound not containing silicon atoms can be used regardless of the type of solvent. Obtain a good surface treatment effect. According to the comparison of Example 6 with Examples 14-21 and Examples 34-52, it can be seen that the use of various compounds as heterocyclic compounds can be related to the improvement of the efficiency of hydrophobization by the silylation agent during surface treatment. The desired effect. In particular, according to Examples 15-19, 34, 37, 39 and 41-50, even when the content of heterocyclic compounds is slightly less, the good hydrophobization effect obtained by the surface treatment agent will not be significant. Damaged.

Claims (4)

一種表面處理劑，其係用於被處理體之表面處理，且包含矽烷基化劑、及不包含矽原子之含氮雜環化合物者，上述矽烷基化劑係下述通式(3)、(4)或(6)~(9)所表示之矽烷基化劑或環狀矽氮烷化合物，上述含氮雜環化合物係包含縮合多環或含氮5員環，且具有芳香性之化合物，上述縮合多環包含含氮5員環骨架，
Figure 105130432-A0305-02-0028-1
 (上述通式(3)中，R4、R5及R6分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R4、R5及R6中所包含之碳原子之合計之個數為1個以上，R7表示氫原子、或者飽和或不飽和烷基，R8表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或者飽和或不飽和雜環烷基，R7及R8可相互鍵結而形成包含氮原子之環結構)；
Figure 105130432-A0305-02-0028-2
 (上述通式(4)中，R4、R5及R6分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R4、R5及R6中所包含之碳原子之合計之個數為1個以上，R9表示氫原子、甲基、三甲基矽烷基或二甲基矽烷基，R10、R11及R12分別獨立地表示氫原子或有機基，R10、R11及R12中所包含之碳原子之合計之個數為1個以上)；
Figure 105130432-A0305-02-0029-3
 (上述通式(6)中，R4、R5及R6分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R4、R5及R6中所包含之碳原子之合計之個數為1個以上，R9表示氫原子、甲基、三甲基矽烷基或二甲基矽烷基，R16表示氫原子、飽和或不飽和烷基、三氟甲基或三烷基矽烷基胺基)；
Figure 105130432-A0305-02-0029-4
 (上述通式(7)中，R17及R18分別獨立地表示氫原子、烷基、三烷基矽烷基，R17及R18中之至少一者表示三烷基矽烷基)；
Figure 105130432-A0305-02-0029-5
 (上述通式(8)中，R19表示三烷基矽烷基，R20及R21分別獨立地表示氫原子或有機基)；
Figure 105130432-A0305-02-0029-6
 (上述通式(9)中，R4、R5及R6分別獨立地表示氫原子、鹵素原子、含氮基或有機基，R4、R5及R6中所包含之碳原子之合計之個數為1個以上，R22表示有機基，R23不存在，或者於存在之情形時，表示-SiR24R25R26，R24、R25及R26分別獨立地表示氫原子、鹵素原子、含氮基或有機基)。 A surface treatment agent, which is used for the surface treatment of the object to be treated and contains a silylation agent and a nitrogen-containing heterocyclic compound that does not contain silicon atoms. The silylation agent is of the following general formula (3), The silylating agent or cyclic silazane compound represented by (4) or (6) to (9), the above nitrogen-containing heterocyclic compound is a compound containing a condensed polycyclic or nitrogen-containing 5-membered ring and having aromaticity , The above-mentioned condensed polycyclic ring contains a nitrogen-containing 5-membered ring skeleton,
Figure 105130432-A0305-02-0028-1
 (In the above general formula (3), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and the total of the carbon atoms contained in R 4 , R 5 and R 6 The number is 1 or more, R 7 represents a hydrogen atom, or a saturated or unsaturated alkyl group, R 8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an acetyl group, or a saturated or Unsaturated heterocycloalkyl, R 7 and R 8 may be bonded to each other to form a ring structure containing a nitrogen atom);
Figure 105130432-A0305-02-0028-2
 (In the above general formula (4), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and the total of the carbon atoms contained in R 4 , R 5 and R 6 The number is one or more, R 9 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R 10 , R 11 and R 12 each independently represent a hydrogen atom or an organic group, R 10 , The total number of carbon atoms contained in R 11 and R 12 is 1 or more);
Figure 105130432-A0305-02-0029-3
 (In the above general formula (6), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and the total of the carbon atoms contained in R 4 , R 5 and R 6 The number is 1 or more, R 9 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, and R 16 represents a hydrogen atom, a saturated or unsaturated alkyl group, a trifluoromethyl group or a trialkyl group Silylamino);
Figure 105130432-A0305-02-0029-4
 (In the above general formula (7), R 17 and R 18 each independently represent a hydrogen atom, an alkyl group, and a trialkylsilyl group, and at least one of R 17 and R 18 represents a trialkylsilyl group);
Figure 105130432-A0305-02-0029-5
 (In the above general formula (8), R 19 represents a trialkylsilyl group, and R 20 and R 21 each independently represent a hydrogen atom or an organic group);
Figure 105130432-A0305-02-0029-6
 (In the above general formula (9), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and the total of the carbon atoms contained in R 4 , R 5 and R 6 The number is one or more, R 22 represents an organic group, R 23 does not exist, or when it exists, represents -SiR 24 R 25 R 26 , R 24 , R 25 and R 26 each independently represent a hydrogen atom, Halogen atom, nitrogen-containing group or organic group). 如請求項1之表面處理劑，其中上述矽烷基化劑係上述通式(3)、(4)或(6)~(8)所表示之矽烷基化劑或環狀矽氮烷化合物。 The surface treatment agent of claim 1, wherein the silylation agent is a silylation agent or a cyclic silazane compound represented by the above general formulas (3), (4) or (6) to (8). 如請求項1或2之表面處理劑，其進而含有溶劑。 Such as the surface treatment agent of claim 1 or 2, which further contains a solvent. 一種表面處理方法，其係使如請求項1至3中任一項之表面處理劑暴露於被處理體之表面，對上述被處理體之表面進行處理。 A surface treatment method, which exposes the surface treatment agent of any one of Claims 1 to 3 to the surface of the object to be treated, and treats the surface of the object to be treated.
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