TW201843731A - Wafer surface processing method and composition for use with said method - Google Patents

Wafer surface processing method and composition for use with said method Download PDF

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TW201843731A
TW201843731A TW107112874A TW107112874A TW201843731A TW 201843731 A TW201843731 A TW 201843731A TW 107112874 A TW107112874 A TW 107112874A TW 107112874 A TW107112874 A TW 107112874A TW 201843731 A TW201843731 A TW 201843731A
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composition
group
wafer
liquid
fluorine
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TW107112874A
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TWI670767B (en
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高田朋宏
照井貴陽
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日商中央硝子股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Abstract

This wafer surface processing method for cleaning a wafer having an irregular pattern on a surface thereof and including Si element at least in the recess, the method comprising a step of forming a water-repellent protection film at least on the recess surface by subjecting the irregular pattern surface to a vapor of a composition in a state in which a liquid is held at least in the recess of the irregular pattern, changing the state of the vapor into a liquid state of the composition on the wafer surface, substituting the liquid of the composition for the liquid held in the recess, and holding the substituted liquid. The method is characterized in that: the composition includes a silylation agent expressed by a general formula (1), and a solvent in which a fluorine-containing ether expressed by a general formula (2) and having a boiling point lower than the boiling point of the silylation agent occupies 99.8 to 100 mass% with respect to a total of 100 mass%; and the amount of the silylation agent with respect to a total amount of the silylation agent and the solvent is 2 to 30 mass%. (1) (R1)y(H)4-x-ySi[N(R2)2]x (2) CnF2n+1-O-CmH2m+1 The composition provides a water-repellency providing effect equivalent to that of conventional art, can be vaporized at a temperature such that thermal decomposition of the silylation agent serving as a protection film forming component is not caused, and can suppress deposition or precipitation of insoluble matter even when the concentration of the silylation agent is not less than 2 mass%.

Description

晶圓之表面處理方法及用於該方法之組合物Wafer surface treatment method and composition for the same

本發明係關於一種於具有Si元素之晶圓之洗淨中使用特定之組合物之蒸氣的晶圓之表面處理方法及該組合物。The present invention relates to a surface treatment method for a wafer using a vapor of a specific composition in the cleaning of a wafer having a Si element, and the composition.

對網路或數位家電用之半導體裝置要求進一步之高性能、高功能化或低耗電化。因此，業界正進行電路圖案之微細化，伴隨微細化進行，電路圖案之圖案崩塌成為問題。於半導體裝置製造中，多使用以粒子或金屬雜質之去除為目的之洗淨步驟，其結果，洗淨步驟占到整個半導體製造步驟之3～4成。於該洗淨步驟中，若半導體裝置之微細化所伴隨之圖案之縱橫比變高，則於洗淨或沖洗後，氣液界面通過圖案時圖案崩壞之現象為圖案崩塌。為了防止圖案崩塌之產生而不得不變更圖案之設計，或會導致生產時之良率下降，因此，期望防止洗淨步驟中之圖案崩塌之方法。 作為防止圖案崩塌之方法，已知於圖案表面形成撥水性保護膜較為有效。該撥水化必須於不使圖案表面乾燥之狀況下進行，因此，利用能夠使圖案表面撥水化之撥水性保護膜形成用藥液來形成撥水性保護膜。 於專利文獻1中，揭示有一種晶圓之處理方法，其特徵在於：其係包含於在表面具有微細之凹凸圖案之矽晶圓之洗淨時，於該凹凸圖案表面導入OH基後，對凹凸圖案表面供給保護膜形成用藥液之蒸氣而形成撥水性保護膜之步驟者，且上述藥液包含： 選自由氫氟醚、氫氯氟烴所組成之群中之至少1種以上之含氟溶劑93.5～97.499質量%； 丙二醇單甲醚乙酸酯2～5質量%； 選自由六甲基二矽氮烷、四甲基二矽氮烷所組成之群中之至少1種以上之矽氮烷化合物0.5～5質量%；及 選自由三氟乙酸、三氟乙酸酐、三氟乙酸三甲基矽烷酯所組成之群中之至少1種以上之酸0.001～0.25質量%。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第5648053號公報Semiconductor devices for network or digital home appliances require further high performance, high functionality, or low power consumption. Therefore, the industry is making the circuit pattern finer, and the pattern collapse of the circuit pattern becomes a problem with the miniaturization. In the manufacture of a semiconductor device, a cleaning step for removing particles or metal impurities is often used. As a result, the cleaning step accounts for 3 to 40% of the entire semiconductor manufacturing step. In the cleaning step, when the aspect ratio of the pattern associated with the miniaturization of the semiconductor device is increased, the pattern collapses when the gas-liquid interface passes through the pattern after the cleaning or rinsing. In order to prevent the occurrence of pattern collapse and to change the design of the pattern, or to cause a decrease in yield during production, it is desirable to prevent the pattern from collapsing in the cleaning step. As a method of preventing pattern collapse, it is known that it is effective to form a water-repellent protective film on the surface of the pattern. This water repellency must be carried out without drying the surface of the pattern. Therefore, the water-repellent protective film is formed by using the water-repellent protective film forming chemical liquid which can hydrate the surface of the pattern. Patent Document 1 discloses a method for processing a wafer, which is characterized in that it is included in a cleaning of a wafer having a fine uneven pattern on its surface, and after introducing an OH group on the surface of the concave-convex pattern, The surface of the concave-convex pattern is supplied with a vapor of the protective film forming chemical liquid to form a water-repellent protective film, and the chemical liquid contains: at least one selected from the group consisting of hydrofluoroether and hydrochlorofluorocarbon; The solvent is 93.5 to 97.499 mass%; the propylene glycol monomethyl ether acetate is 2 to 5% by mass; and at least one of the group consisting of hexamethyldiazepine and tetramethyldiazepine is selected. The alkyl compound is 0.5 to 5% by mass; and at least one or more selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, and trimethyl decyl trifluoroacetate is 0.001 to 0.25% by mass. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 5648053

[發明所欲解決之問題] 專利文獻1中記載之晶圓之處理方法係一次性實施複數片晶圓之洗淨處理，為對半導體晶圓之洗淨製程之效率化有效之方法，但由於含有沸點高於作為保護膜形成成分之矽氮烷化合物之沸點(六甲基二矽氮烷之沸點：約125℃、四甲基二矽氮烷之沸點：約100℃)之丙二醇單甲醚乙酸酯(沸點：約146℃)作為必須成分，故使藥液快速全量蒸氣化時必須以該丙二醇單甲醚乙酸酯之沸點以上之溫度(即較矽氮烷化合物之沸點高20℃以上之溫度)施加充分之熱量。因此，根據上述方法，有蒸氣化時引起矽氮烷化合物之熱分解之虞。 因此，藥液中所含有之溶劑較理想為使用沸點低於保護膜形成成分之沸點者。其原因在於：只要為此種溶劑與保護膜形成成分之組合，則能夠將上述蒸氣化之溫度控制於保護膜形成成分之沸點附近(保護膜形成成分之沸點＋5℃左右)，因此，無引起蒸氣化所伴隨之保護膜形成成分之熱分解之虞。又，當使藥液蒸氣化時，就安全性之觀點而言，較理想為佔據該蒸氣之大部分之溶劑之引火點較高(阻燃性或不燃性)。作為如上述般滿足低沸點且高引火點(阻燃性或不燃性)之溶劑，可列舉含氟醚系之溶劑。 但，本發明人等進行了努力研究，結果發現，若僅單純地將先前之矽烷化劑與沸點低於其之含氟醚系溶劑組合，則存在因兩者之組合而藥液之穩定性較低，尤其是於矽烷化劑之濃度為2質量%以上之藥液中容易產生不溶物之析出或沈澱之問題。 因此，於本發明中，課題在於提供一種發揮與先前同等之撥水性賦予效果並且解決上述問題之組合物，及提供一種於具有Si元素之晶圓之洗淨中使用該組合物之蒸氣之晶圓之表面處理方法。 [解決問題之技術手段] 本發明提供一種晶圓之表面處理方法，其包含於在表面具有凹凸圖案且至少於該凹部具有Si元素之晶圓(以下，存在簡記作「晶圓」之情形)之洗淨中，於在上述凹凸圖案之至少凹部保持有液體之狀態下，將溶液狀態之組合物(以下，存在簡記作「組合物」之情形)之蒸氣供至上述凹凸圖案表面，於晶圓表面使該蒸氣狀態變化為上述組合物之液體狀態，將上述凹部所保持之液體置換為該組合物之液體並保持，藉此至少於上述凹部表面形成撥水性保護膜(以下，存在簡記作「保護膜」之情形)之步驟，且 上述組合物包含： 下述通式[1]所表示之矽烷化劑；及 沸點低於上述矽烷化劑之沸點之下述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑， 該矽烷化劑之量相對於上述矽烷化劑與溶劑之總量為2～30質量%，[式[1]中，R1 分別相互獨立地為選自碳數為1～10之烴基、及氫元素之一部分或全部被取代為氟元素之碳數為1～8之烴基中之基，R2 分別相互獨立地為選自氫元素之一部分或全部可取代為氟元素之甲基、乙基、乙醯基中之基。x為1～3之整數，y為1～3之整數，4－x－y為0～2之整數]，[式[2]中，Cn F2n ＋ 1 表示碳數n＝4～5之直鏈狀之全氟烷基，Cm H2m ＋ 1 表示碳數m＝2～6之直鏈狀或分枝狀之烷基]。 於上述晶圓之表面處理方法中，上述矽烷化劑較佳為選自由(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、C11 H23 Si(CH3 )2 N(CH3 )2 、C12 H25 Si(CH3 )2 N(CH3 )2 、C13 H27 Si(CH3 )2 N(CH3 )2 、C14 H29 Si(CH3 )2 N(CH3 )2 、C15 H31 Si(CH3 )2 N(CH3 )2 、C16 H33 Si(CH3 )2 N(CH3 )2 、C17 H35 Si(CH3 )2 N(CH3 )2 、C18 H37 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(N(CH3 )2 )3 、C2 F5 CH2 CH2 Si(N(CH3 )2 )3 、C3 F7 CH2 CH2 Si(N(CH3 )2 )3 、C4 F9 CH2 CH2 Si(N(CH3 )2 )3 、C5 F11 CH2 CH2 Si(N(CH3 )2 )3 、C6 F13 CH2 CH2 Si(N(CH3 )2 )3 、C7 F15 CH2 CH2 Si(N(CH3 )2 )3 、C8 F17 CH2 CH2 Si(N(CH3 )2 )3 、CF3 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C2 F5 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C3 F7 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C4 F9 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C5 F11 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C6 F13 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C7 F15 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C8 F17 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或上述二甲基胺基矽烷之二甲基胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物所組成之群中之至少1種。 於上述晶圓之表面處理方法中，上述通式[1]之-N(R2 )2 所表示之基更佳為-N(CH3 )2 基或-N(C2 H5 )2 基。 於上述晶圓之表面處理方法中，上述矽烷化劑尤佳為選自由三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺所組成之群中之至少1種。 於上述晶圓之表面處理方法中，上述含氟醚較佳為九氟-正丁基乙基醚。 於上述晶圓之表面處理方法中，上述組合物中之上述矽烷化劑與上述含氟醚之質量比(矽烷化劑/含氟醚)較佳為1/99～30/70。 於上述晶圓之表面處理方法中，上述組合物較佳為由上述矽烷化劑及上述含氟醚構成。 於上述晶圓之表面處理方法中，上述組合物亦可進而包含酸。 於上述晶圓之表面處理方法中，上述組合物亦可為由上述矽烷化劑、上述含氟醚及酸構成者。 於上述晶圓之表面處理方法中，上述組合物中可包含之酸較佳為選自由三氟乙酸三甲基矽烷酯、三氟甲磺酸三甲基矽烷酯、三氟乙酸二甲基矽烷酯、三氟甲磺酸二甲基矽烷酯、三氟乙酸丁基二甲基矽烷酯、三氟甲磺酸丁基二甲基矽烷酯、三氟乙酸己基二甲基矽烷酯、三氟甲磺酸己基二甲基矽烷酯、三氟乙酸辛基二甲基矽烷酯、三氟甲磺酸辛基二甲基矽烷酯、三氟乙酸癸基二甲基矽烷酯、及三氟甲磺酸癸基二甲基矽烷酯所組成之群中之至少1種。 於上述晶圓之表面處理方法中，上述凹部所保持之液體較佳為非水溶劑。 於上述晶圓之表面處理方法中，較佳為至少於上述凹部表面形成撥水性保護膜後，將該凹部所保持之液體狀態之上述組合物藉由乾燥而去除。藉由該乾燥，將上述組合物中之溶劑或無助於保護膜之形成之多餘矽烷化劑等去除。 於上述晶圓之表面處理方法中，較佳為至少於上述凹部表面形成撥水性保護膜後，將該凹部所保持之液體狀態之上述組合物置換為與該組合物不同之洗淨液，並將該洗淨液藉由乾燥而去除。 於上述晶圓之表面處理方法中，亦可於上述乾燥後之晶圓表面實施選自由加熱處理、光照射處理、臭氧暴露處理、電漿照射處理、及電暈放電處理所組成之群中之至少1種處理而將上述撥水性保護膜去除。 又，本發明提供一種組合物，其於在表面具有凹凸圖案且至少於該凹部具有Si元素之晶圓之洗淨中，於在上述凹凸圖案之至少凹部保持有液體之狀態下，以蒸氣之形式供至該凹凸圖案表面，於晶圓表面自蒸氣狀態變化為液體狀態，取代上述凹部所保持之液體並保持於該凹部，其包含： 下述通式[1]所表示之矽烷化劑，及 沸點低於上述矽烷化劑之沸點之下述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑， 該矽烷化劑之量相對於上述矽烷化劑與溶劑之總量為2～30質量%，[式[1]中，R1 分別相互獨立地為選自碳數為1～10之烴基、及氫元素之一部分或全部被取代為氟元素之碳數為1～8之烴基中之基，R2 分別相互獨立地為選自氫元素之一部分或全部可取代為氟元素之甲基、乙基、乙醯基中之基。x為1～3之整數，y為1～3之整數，4－x－y為0～2之整數]，[式[2]中，Cn F2n ＋ 1 表示碳數n＝4～5之直鏈狀之全氟烷基，Cm H2m ＋ 1 表示碳數m＝2～6之直鏈狀或分枝狀之烷基]。 於上述組合物中，上述矽烷化劑較佳為選自由(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、C11 H23 Si(CH3 )2 N(CH3 )2 、C12 H25 Si(CH3 )2 N(CH3 )2 、C13 H27 Si(CH3 )2 N(CH3 )2 、C14 H29 Si(CH3 )2 N(CH3 )2 、C15 H31 Si(CH3 )2 N(CH3 )2 、C16 H33 Si(CH3 )2 N(CH3 )2 、C17 H35 Si(CH3 )2 N(CH3 )2 、C18 H37 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(N(CH3 )2 )3 、C2 F5 CH2 CH2 Si(N(CH3 )2 )3 、C3 F7 CH2 CH2 Si(N(CH3 )2 )3 、C4 F9 CH2 CH2 Si(N(CH3 )2 )3 、C5 F11 CH2 CH2 Si(N(CH3 )2 )3 、C6 F13 CH2 CH2 Si(N(CH3 )2 )3 、C7 F15 CH2 CH2 Si(N(CH3 )2 )3 、C8 F17 CH2 CH2 Si(N(CH3 )2 )3 、CF3 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C2 F5 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C3 F7 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C4 F9 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C5 F11 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C6 F13 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C7 F15 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C8 F17 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或上述二甲基胺基矽烷之二甲基胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物所組成之群中之至少1種。 於上述組合物中，上述通式[1]之-N(R2 )2 所表示之基更佳為-N(CH3 )2 基或-N(C2 H5 )2 基。 於上述組合物中，上述矽烷化劑尤佳為選自由三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺所組成之群中之至少1種。 於上述組合物中，上述含氟醚較佳為九氟-正丁基乙基醚。 上述組合物中之上述矽烷化劑與上述含氟醚之質量比(矽烷化劑/含氟醚)較佳為1/99～30/70。 上述組合物較佳為由上述矽烷化劑及上述含氟醚構成。 又，上述組合物亦可進而包含酸。 又，上述組合物亦可為由上述矽烷化劑、上述含氟醚及酸構成者。 又，上述組合物中可包含之酸較佳為選自由三氟乙酸三甲基矽烷酯、三氟甲磺酸三甲基矽烷酯、三氟乙酸二甲基矽烷酯、三氟甲磺酸二甲基矽烷酯、三氟乙酸丁基二甲基矽烷酯、三氟甲磺酸丁基二甲基矽烷酯、三氟乙酸己基二甲基矽烷酯、三氟甲磺酸己基二甲基矽烷酯、三氟乙酸辛基二甲基矽烷酯、三氟甲磺酸辛基二甲基矽烷酯、三氟乙酸癸基二甲基矽烷酯、及三氟甲磺酸癸基二甲基矽烷酯所組成之群中之至少1種。 [發明之效果] 根據本發明，可提供一種發揮與先前同等之撥水性賦予效果並且能夠於無引起作為保護膜形成成分之矽烷化劑之熱分解之虞的溫度下蒸氣化，即便矽烷化劑之濃度為2質量%以上亦可抑制不溶物之析出或沈澱的組合物，及於具有Si元素之晶圓之洗淨中使用該組合物之蒸氣的晶圓之表面處理方法。[Problem to be Solved by the Invention] The method of processing a wafer described in Patent Document 1 is a method of performing a cleaning process of a plurality of wafers at a time, and is effective for improving the efficiency of a semiconductor wafer cleaning process, but Propylene glycol monomethyl ether having a boiling point higher than the boiling point of the indazane compound as a protective film forming component (boiling point of hexamethyldioxane: about 125 ° C, boiling point of tetramethyldiazepine: about 100 ° C) Acetate (boiling point: about 146 ° C) is an essential component, so the rapid vaporization of the liquid must be at a temperature above the boiling point of the propylene glycol monomethyl ether acetate (ie, 20 ° C higher than the boiling point of the hydrazine compound). The above temperature) applies sufficient heat. Therefore, according to the above method, there is a possibility of causing thermal decomposition of the indazane compound upon vaporization. Therefore, it is preferred that the solvent contained in the chemical liquid be a boiling point lower than the boiling point of the protective film forming component. The reason for this is that the combination of the solvent and the protective film forming component can control the vaporization temperature to be near the boiling point of the protective film forming component (the boiling point of the protective film forming component is about +5° C.), so that it is not caused. The thermal decomposition of the protective film forming component accompanying vaporization. Further, when the chemical liquid is vaporized, it is preferable that the ignition point of the solvent occupying most of the vapor is high (flame retardancy or nonflammability) from the viewpoint of safety. As a solvent which satisfies the low boiling point and the high ignition point (flame retardance or nonflammability) as mentioned above, a fluorine-containing ether type solvent is mentioned. However, the inventors of the present invention conducted diligent research and found that if only the former decylating agent is simply combined with a fluorinated ether solvent having a boiling point lower than that, the stability of the chemical solution due to the combination of the two is present. The problem is that the precipitation or precipitation of insoluble matter is liable to occur in a chemical solution having a concentration of the alkylating agent of 2% by mass or more. Therefore, in the present invention, it is an object of the invention to provide a composition which exhibits the same water repellency imparting effect as before and solves the above problems, and provides a crystal of a vapor which uses the composition in the cleaning of a wafer having a Si element. Round surface treatment method. [Means for Solving the Problems] The present invention provides a surface treatment method for a wafer, which is included in a wafer having a concave-convex pattern on its surface and having Si element at least in the concave portion (hereinafter, abbreviated as "wafer") In the cleaning, the vapor in the solution state (hereinafter, abbreviated as "composition") is supplied to the surface of the concave-convex pattern in a state where at least the concave portion of the concave-convex pattern is kept in a liquid state. The circular surface changes the vapor state to the liquid state of the composition, and the liquid held by the concave portion is replaced with the liquid of the composition and held, thereby forming a water-repellent protective film on at least the surface of the concave portion (hereinafter, there is a shorthand note) a step of the "protective film", wherein the composition comprises: a decylating agent represented by the following formula [1]; and a formula represented by the following formula [2] having a boiling point lower than a boiling point of the above-mentioned decylating agent The amount of the fluorinated ether is from 99.8 to 100% by mass based on 100% by mass of the total amount, and the amount of the decylating agent is from 2 to 30% by mass based on the total amount of the sulfonating agent and the solvent. [In the formula [1], R 1 is each independently a hydrocarbon group selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydrocarbon group having a carbon number of 1 to 8 partially or wholly substituted with a fluorine element. R 2 is each independently a group selected from a methyl group, an ethyl group or an ethyl fluorenyl group which is partially or wholly substituted with a fluorine element. x is an integer from 1 to 3, y is an integer from 1 to 3, and 4-x-y is an integer from 0 to 2], [In the formula [2], C n F 2n + 1 represents a linear perfluoroalkyl group having a carbon number n = 4 to 5, and C m H 2m + 1 represents a linear number of carbon number m = 2 to 6 or Branched alkyl]. In the surface treatment method of the above wafer, the above sulfonating agent is preferably selected from the group consisting of (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 4 H 9 ) 3 SiN(CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si(CH 3 ) 2 N(CH 3 ) 2 , C 11 H 23 Si(CH 3 ) 2 N(CH 3 ) 2 , C 12 H 25 Si(CH 3 ) 2 N(CH 3 ) 2 , C 13 H 27 Si(CH 3 ) 2 N(CH 3 ) 2 , C 14 H 29 Si(CH 3 ) 2 N(CH 3 ) 2 , C 15 H 31 Si(CH 3 ) 2 N(CH 3 ) 2 , C 16 H 33 Si(CH 3 ) 2 N(CH 3 ) 2 , C 17 H 35 Si(CH 3 ) 2 N(CH 3 ) 2 , C 18 H 37 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 ) 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N(CH 3 ) 2 , C 2 H 5 Si(H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 )( H) N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H)N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si (N(CH 3 ) 2 ) 3 , C 2 F 5 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 3 F 7 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 4 F 9 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 5 F 11 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 6 F 13 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 7 F 15 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 8 F 17 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , CF 3 CH 2 CH 2 Si (CH 3 )(N(CH 3 ) 2 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) (N(CH 3 ) 2 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 )(N(CH) 3 ) 2 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si( CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 , or the dimethylamino group of the above dimethylamino decane (-N(CH 3 ) 2 group) is - At least one of the group consisting of N(C 2 H 5 ) 2 , -N(CH 3 )C(O)CH 3 , and -N(CH 3 )C(O)CF 3 . In the surface treatment method of the above wafer, the group represented by -N(R 2 ) 2 of the above formula [1] is more preferably -N(CH 3 ) 2 group or -N(C 2 H 5 ) 2 group. . In the surface treatment method of the wafer, the decylating agent is preferably at least one selected from the group consisting of trimethyldecyldimethylamine and trimethyldecyldiethylamine. In the surface treatment method of the above wafer, the fluorine-containing ether is preferably nonafluoro-n-butyl ethyl ether. In the surface treatment method of the above wafer, the mass ratio of the above-mentioned decylating agent to the above-mentioned fluorine-containing ether (the alkylating agent/fluorine-containing ether) is preferably from 1/99 to 30/70. In the surface treatment method of the above wafer, the composition is preferably composed of the above-described decylating agent and the above-mentioned fluorine-containing ether. In the surface treatment method of the above wafer, the above composition may further comprise an acid. In the above surface treatment method for a wafer, the composition may be composed of the above-described decylating agent, the above-mentioned fluorine-containing ether, and an acid. In the surface treatment method of the above wafer, the acid which may be contained in the above composition is preferably selected from the group consisting of trimethyl decyl trifluoroacetate, trimethyl decyl trifluoromethanesulfonate, and dimethyl decane trifluoroacetate. Ester, dimethyl decyl trifluoromethanesulfonate, butyl dimethyl decyl trifluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, trifluoromethyl Hexyl dimethyl decyl sulfonate, octyl dimethyl decyl trifluoroacetate, octyl dimethyl decyl trifluoromethane sulfonate, decyl dimethyl decyl trifluoroacetate, and bismuth triflate At least one of the group consisting of dimethyl decyl esters. In the surface treatment method of the wafer, the liquid held by the concave portion is preferably a nonaqueous solvent. In the surface treatment method of the wafer, it is preferable that the water-repellent protective film is formed on at least the surface of the concave portion, and the composition in a liquid state held by the concave portion is removed by drying. By the drying, the solvent in the above composition or the excess decylating agent or the like which does not contribute to the formation of the protective film is removed. In the surface treatment method of the wafer, it is preferable that at least the water-repellent protective film is formed on the surface of the concave portion, and the composition in a liquid state held by the concave portion is replaced with a cleaning liquid different from the composition, and The cleaning solution was removed by drying. In the surface treatment method of the wafer, the surface of the dried wafer may be subjected to a group selected from the group consisting of heat treatment, light irradiation treatment, ozone exposure treatment, plasma irradiation treatment, and corona discharge treatment. The water-repellent protective film is removed by at least one treatment. Moreover, the present invention provides a composition in which a wafer having a concave-convex pattern on a surface and at least a wafer having a Si element in the concave portion is in a state in which a liquid is held in at least a concave portion of the concave-convex pattern. The form is supplied to the surface of the concave-convex pattern, and changes from a vapor state to a liquid state on the surface of the wafer, and the liquid held by the concave portion is held in the concave portion, and comprises: a decylating agent represented by the following general formula [1], And a solvent having a boiling point lower than the boiling point of the above-mentioned decylating agent, wherein the fluorinated ether represented by the following formula [2] is 99.8 to 100% by mass based on 100% by mass of the total amount, and the amount of the decylating agent is relative to the above The total amount of the alkylating agent and the solvent is 2 to 30% by mass, [In the formula [1], R 1 is each independently a hydrocarbon group selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydrocarbon group having a carbon number of 1 to 8 partially or wholly substituted with a fluorine element. R 2 is each independently a group selected from a methyl group, an ethyl group or an ethyl fluorenyl group which is partially or wholly substituted with a fluorine element. x is an integer from 1 to 3, y is an integer from 1 to 3, and 4-x-y is an integer from 0 to 2], [In the formula [2], C n F 2n + 1 represents a linear perfluoroalkyl group having a carbon number n = 4 to 5, and C m H 2m + 1 represents a linear number of carbon number m = 2 to 6 or Branched alkyl]. In the above composition, the above decylating agent is preferably selected from the group consisting of (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 4 H 9 ) 3 SiN(CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH 3 2 N(CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si(CH 3 ) 2 N(CH 3 ) 2 , C 11 H 23 Si(CH 3 ) 2 N(CH 3 ) 2 , C 12 H 25 Si(CH 3 ) 2 N(CH 3 ) 2 , C 13 H 27 Si( CH 3 ) 2 N(CH 3 ) 2 , C 14 H 29 Si(CH 3 ) 2 N(CH 3 ) 2 , C 15 H 31 Si(CH 3 ) 2 N(CH 3 ) 2 , C 16 H 33 Si (CH 3 ) 2 N(CH 3 ) 2 , C 17 H 35 Si(CH 3 ) 2 N(CH 3 ) 2 , C 18 H 37 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 ) 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N(CH 3 ) 2 , C 2 H 5 Si( H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 )(H)N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H)N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 2 F 5 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 3 F 7 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 4 F 9 CH 2 CH 2 Si(N(CH) 3 ) 2 ) 3 , C 5 F 11 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 6 F 13 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 7 F 15 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 8 F 17 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , CF 3 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 8 F 17 CH 2 CH 2 Si (CH 3 )(N(CH 3 ) 2 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 or the dimethylamino group of the above dimethylamino decane (-N(CH 3 ) 2 group) is -N(C 2 H 5 ) 2 , At least one of the group consisting of -N(CH 3 )C(O)CH 3 and -N(CH 3 )C(O)CF 3 . In the above composition, the group represented by -N(R 2 ) 2 of the above formula [1] is more preferably an -N(CH 3 ) 2 group or a -N(C 2 H 5 ) 2 group. In the above composition, the above-mentioned decylating agent is preferably at least one selected from the group consisting of trimethyldecyldimethylamine and trimethyldecyldiethylamine. In the above composition, the above fluorine-containing ether is preferably nonafluoro-n-butylethyl ether. The mass ratio of the above decylating agent to the above-mentioned fluorine-containing ether in the above composition (the alkylating agent/fluorine-containing ether) is preferably from 1/99 to 30/70. The above composition is preferably composed of the above-described decylating agent and the above-mentioned fluorine-containing ether. Further, the above composition may further contain an acid. Further, the composition may be composed of the above-described decylating agent, the above-mentioned fluorine-containing ether, and an acid. Further, the acid which may be contained in the above composition is preferably selected from the group consisting of trimethyl decyl trifluoroacetate, trimethyl decyl trifluoromethanesulfonate, dimethyl decyl trifluoroacetate, and trifluoromethanesulfonic acid Methyl decyl ester, butyl dimethyl decyl trifluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, hexyl dimethyl decyl trifluoromethanesulfonate , octyl dimethyl decyl trifluoroacetate, octyl dimethyl decyl trifluoromethanesulfonate, decyl dimethyl decyl trifluoroacetate, and decyl dimethyl decyl triflate At least one of the groups. [Effects of the Invention] According to the present invention, it is possible to provide a vaporization at a temperature which exhibits the same water repellency imparting effect as that of the prior art and which can cause thermal decomposition of the decylating agent which is a protective film forming component, even if the alkylating agent A composition which can suppress precipitation or precipitation of insoluble matter by a concentration of 2% by mass or more, and a surface treatment method of a wafer using the vapor of the composition in cleaning of a wafer having Si element.

(1)關於本發明之組合物 本發明之組合物係於在表面具有凹凸圖案且至少於該凹部具有Si元素之晶圓之洗淨中，於在上述凹凸圖案之至少凹部保持有液體之狀態下，以蒸氣之形式供至該凹凸圖案表面者，其於上述晶圓表面自蒸氣狀態變化為液體狀態，置換原本保持於凹部之液體。而且，藉由該置換而於上述凹部保持液體狀態之組合物，藉此，於該凹部表面形成撥水性保護膜。 本發明之組合物包含： 下述通式[1]所表示之矽烷化劑；及 沸點低於上述矽烷化劑之沸點之下述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑，且 該矽烷化劑之量相對於上述矽烷化劑與溶劑之總量為2～30質量%，[式[1]中，R1 分別相互獨立地為選自碳數為1～10之烴基、及氫元素之一部分或全部被取代為氟元素之碳數為1～8之烴基中之基，R2 分別相互獨立地為選自氫元素之一部分或全部可取代為氟元素之甲基、乙基、乙醯基中之基。x為1～3之整數，y為1～3之整數，4－x－y為0～2之整數]，[式[2]中，Cn F2n ＋ 1 表示碳數n＝4～5之直鏈狀之全氟烷基，Cm H2m ＋ 1 表示碳數m＝2～6之直鏈狀或分枝狀之烷基]。 於上述通式[1]所表示之矽烷化劑中，(R1 )y (H)4 － x － y Si係具有撥水性之官能基之部位。而且，上述矽烷化劑與晶圓表面之矽烷醇基進行反應，上述具有撥水性之官能基之部位被固定於晶圓表面，藉此，於該晶圓表面形成撥水性之保護膜。於組合物進而包含酸之情形時，藉由該酸，上述矽烷化劑與晶圓表面快速反應，而容易獲得撥水性賦予效果。 作為上述矽烷化劑之具體例，可列舉(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、C11 H23 Si(CH3 )2 N(CH3 )2 、C12 H25 Si(CH3 )2 N(CH3 )2 、C13 H27 Si(CH3 )2 N(CH3 )2 、C14 H29 Si(CH3 )2 N(CH3 )2 、C15 H31 Si(CH3 )2 N(CH3 )2 、C16 H33 Si(CH3 )2 N(CH3 )2 、C17 H35 Si(CH3 )2 N(CH3 )2 、C18 H37 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(N(CH3 )2 )3 、C2 F5 CH2 CH2 Si(N(CH3 )2 )3 、C3 F7 CH2 CH2 Si(N(CH3 )2 )3 、C4 F9 CH2 CH2 Si(N(CH3 )2 )3 、C5 F11 CH2 CH2 Si(N(CH3 )2 )3 、C6 F13 CH2 CH2 Si(N(CH3 )2 )3 、C7 F15 CH2 CH2 Si(N(CH3 )2 )3 、C8 F17 CH2 CH2 Si(N(CH3 )2 )3 、CF3 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C2 F5 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C3 F7 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C4 F9 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C5 F11 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C6 F13 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C7 F15 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C8 F17 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或上述二甲基胺基矽烷之二甲基胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物等。 其中，選自由三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺所組成之群中之至少1種撥水性賦予效果更優異，故而較佳。 上述矽烷化劑之中，上述通式[1]之-N(R2 )2 所表示之基若為-N(CH3 )2 基或-N(C2 H5 )2 基，則與晶圓表面之反應尤其快速，故而較佳。 關於上述組合物中包含之溶劑，總量100質量%之中，包含99.8～100質量%之沸點低於上述矽烷化劑之沸點之上述通式[2]所表示之含氟醚。若使組合物中大量(超過0.2質量%)含有具有上述矽烷化劑之沸點以上之沸點之溶劑，則有於蒸氣化時引起矽烷化劑之熱分解之虞。如上述般，其原因在於：於將組合物全量蒸氣化(直至高沸點溶劑全量蒸發)之前，有由於對矽烷化劑施加過度之高溫或熱量而引起熱分解之虞。又，藉由使用如上述之特定之矽烷化劑及溶劑，而於蒸氣化前之組合物中，矽烷化劑難以分解(組合物之穩定性較高)，能夠使不溶物之析出或沈澱難以產生。 就難以產生不溶物之析出或沈澱之觀點而言，上述組合物中包含之溶劑進而較佳為僅為上述含氟醚。 作為上述含氟醚，就難以產生不溶物之析出或沈澱之觀點而言，可較佳地例示九氟-正丁基乙基醚。 當然，作為上述組合物中包含之矽烷化劑及含氟醚之組合，選擇含氟醚之沸點低於矽烷化劑之沸點之組合。進而，關於上述組合物中包含之矽烷化劑及含氟醚，若兩者之沸點之差為20℃以內，則兩成分容易同時沸騰、蒸發，故而尤佳。 上述組合物中包含之溶劑亦可包含上述含氟醚以外之溶劑(以下，存在簡記作「其他溶劑」之情形)。作為其他溶劑之具體例，可列舉不符合上述通式[2]之含氟醚(例如，九氟-正丁基甲基醚[C4 F9 -O-CH3 ](沸點約61℃，3M製造之Novec7100)、1,1,1,2,2,3,4,5,5,5-十氟-3-甲氧基-4-(三氟甲基)-戊烷[C2 F5 CF(OCH3 )CF(CF3 )2 ](沸點約98℃，3M製造之Novec7300)等)或環己烷等。 矽烷化劑之量相對於上述矽烷化劑與溶劑之總量(以下，存在簡記作「矽烷化劑濃度」之情形)為2～30質量%。若為2質量%以上，則能夠發揮撥水性賦予效果。又，若為30質量%以下，則能夠抑制對洗淨裝置之樹脂製構件等之影響。若為3質量%以上，則容易發揮更優異之撥水性賦予效果，故而較佳。又，若為20質量%以下，則對洗淨裝置之樹脂製構件等之影響進一步變小，價格亦可得到抑制，故而較佳。該濃度進而較佳為5～10質量%。 又，上述組合物若為由上述矽烷化劑及上述含氟醚構成者，則容易使組合物中之全部成分蒸氣化，能夠抑制因組合物中之矽烷化劑之反應引起之變質，能夠提高該組合物之引火點，故而較佳。 另一方面，上述組合物亦可進而包含酸。如上述般，藉由酸，上述矽烷化劑與晶圓表面快速反應，而容易獲得撥水性賦予效果。 作為酸之具體例，可列舉：三氟乙酸三甲基矽烷酯、三氟甲磺酸三甲基矽烷酯、三氟乙酸二甲基矽烷酯、三氟甲磺酸二甲基矽烷酯、三氟乙酸丁基二甲基矽烷酯、三氟甲磺酸丁基二甲基矽烷酯、三氟乙酸己基二甲基矽烷酯、三氟甲磺酸己基二甲基矽烷酯、三氟乙酸辛基二甲基矽烷酯、三氟甲磺酸辛基二甲基矽烷酯、三氟乙酸癸基二甲基矽烷酯、及三氟甲磺酸癸基二甲基矽烷酯等。 上述酸之中，由於保存穩定性優異，故尤佳為三氟乙酸三甲基矽烷酯。 於上述組合物進而包含酸之情形時，酸之量相對於上述矽烷化劑、溶劑及酸之總量(以下，存在簡記作「酸濃度」之情形)較佳為0.01～30質量%。就撥水性賦予效果之觀點而言，該濃度更佳為0.05～20質量%。 上述酸亦可為上述矽烷化劑與酸化合物進行反應而生成者。例如，若使用作為矽烷化劑之三甲基矽烷基二甲基胺及作為酸化合物之三氟乙酸酐作為組合物之原料，則於溶劑中，兩者進行反應而生成三氟乙酸三甲基矽烷酯，其於組合物中作為酸發揮功能。再者，於使用藉由反應生成之酸之情形時，重要的是相較於作為原料之酸化合物(於上述情形時為三氟乙酸酐)，過量裝入作為原料之矽烷化劑(於上述情形時為三甲基矽烷基二甲基胺)。必須以於上述反應之結果所獲得之組合物中，該矽烷化劑之量相對於上述矽烷化劑與溶劑之總量成為2～30質量%之方式裝入。 作為上述酸化合物，例如可列舉三氟乙酸、三氟乙酸酐、三氟甲磺酸、三氟甲磺酸酐，尤佳為三氟乙酸酐。 本發明之組合物亦可包含抗氧化劑等添加劑以進一步提高穩定性。例如，可列舉：4-甲氧基苯酚、二丁基羥基甲苯、丁基羥基苯甲醚、1,4-苯二酚、2-(1,1-二甲基乙基)-1,4-苯二酚、1,4-苯醌、1-辛硫醇、1-壬硫醇、1-癸硫醇、1-十一烷硫醇、1-十二烷硫醇、辛基-3,5-二-第三丁基-4-羥基-氫肉桂酸(例如，BASF製造之Irganox1135)、6-第三丁基-2,4-二甲苯酚等。 又，就組合物之清潔度之觀點而言，上述添加劑較佳為液體，例如較佳為於25℃大氣壓下為液體之1-十二烷硫醇、辛基-3,5-二-第三丁基-4-羥基-氫肉桂酸(例如，BASF製造之Irganox1135)、6-第三丁基-2,4-二甲苯酚等。 又，上述組合物之起始原料中之水分之總量相對於該原料之總量較佳為2000質量ppm以下。於水分量之總量超過2000質量ppm之情形時，上述矽烷化劑之效果下降(於含有酸之情形時，酸之效果亦下降)，不易於短時間內形成上述保護膜。因此，上述組合物原料中之水分量之總量越少越佳，尤佳為500質量ppm以下，進而較佳為200質量ppm以下。進而，若水之存在量較多，則上述組合物之保管穩定性容易下降，因此，水分量較佳為較少，較佳為100質量ppm以下，進而較佳為50質量ppm以下。再者，雖上述水分量越少則越佳，但只要為上述含量範圍內，則上述組合物原料中之水分量亦可為0.1質量ppm以上。因此，上述組合物中包含之矽烷化劑或溶劑較佳為不大量含水者。 又，上述組合物中，液相下利用光散射式液中粒子檢測器進行之粒子測定中，大於0.2 μm之粒子之數量較佳為該組合物每1 mL為100個以下。若上述大於0.2 μm之粒子之數量為該組合物每1 mL超過100個，則有因粒子誘發圖案損傷之虞，而成為引起裝置之良率下降及可靠性下降之原因，故而欠佳。又，可能污染蒸氣處理裝置內，使裝置之良率進一步下降及可靠性進一步下降。又，大於0.2 μm之粒子之數量若為該組合物每1 mL為100個以下，則能夠省略或減少形成上述保護膜後之利用溶劑或水進行之該晶圓表面(保護膜表面)之洗淨，故而較佳。再者，雖上述大於0.2 μm之粒子之數量越少則越佳，但只要為上述含量範圍內，則亦可為該組合物每1 mL為1個以上。再者，本發明中之組合物中，液相下之粒子測定係利用以雷射為光源之光散射式液中粒子測定方式中之市售之測定裝置進行測定者，粒子之粒徑係指PSL(聚苯乙烯製乳膠)標準粒子基準之光散射當量徑。 此處，上述粒子係指原料中以雜質之形式包含之塵、埃、有機固形物、無機固形物等在粒子或組合物之製備中以污染物之形式帶入之塵、埃、有機固形物、無機固形物等粒子等，屬於最終未於組合物中溶解而以粒子之形式存在者。 又，上述組合物中之Na、Mg、K、Ca、Mn、Fe、Cu、Li、Al、Cr、Ni、Zn及Ag之各元素(金屬雜質)之含量相對於該組合物總量較佳為各0.1質量ppb以下。若上述金屬雜質含量相對於該組合物總量超過0.1質量ppb，則有使裝置之接合漏電流增大之虞，而成為引起裝置之良率下降及可靠性下降之原因，故而欠佳。又，可能污染蒸氣處理裝置內，使裝置之良率進一步下降及可靠性進一步下降。又，若上述金屬雜質含量相對於該組合物總量為各0.1質量ppb以下，則能夠省略或減少於晶圓表面形成上述保護膜後之利用溶劑或水進行之該晶圓表面(保護膜表面)之洗淨，故而較佳。因此，雖上述金屬雜質含量越少則越佳，但只要為上述含量範圍內，則相對於該組合物之總量，各元素亦可為0.001質量ppb以上。 (2)關於撥水性保護膜 於本發明中，撥水性保護膜係指藉由形成於晶圓表面而降低該晶圓表面之潤濕性之膜，即賦予撥水性之膜。於本發明中，撥水性係指使物品表面之表面能量降低，而使水或其他液體與該物品表面之間(界面)之相互作用、例如氫鍵、分子間力等減少。尤其是針對水使相互作用減少之效果較大，但對於水與水以外之液體之混合液或水以外之液體亦具有使相互作用減少之效果。藉由該相互作用之減少，能夠增大液體相對於物品表面之接觸角。再者，撥水性保護膜可為由上述矽烷化劑形成者，亦可為包含以矽烷化劑為主成分之反應物者。 (3)關於晶圓 作為上述晶圓，包含於晶圓表面形成有矽、氧化矽、或氮化矽等包含Si元素之膜者或於形成上述凹凸圖案時該凹凸圖案之表面之至少一部分為矽、氧化矽、或氮化矽等包含Si元素者。再者，能夠由上述組合物形成保護膜的是上述凹凸圖案中之包含Si元素之部分之表面。 一般而言，為了獲得於表面具有微細之凹凸圖案之晶圓，首先，於平滑之晶圓表面塗佈抗蝕劑之後，介隔抗蝕劑遮罩對抗蝕劑進行曝光，將經曝光之抗蝕劑、或未曝光之抗蝕劑蝕刻去除，藉此，製作具有所需之凹凸圖案之抗蝕劑。又，藉由將具有圖案之塑模壓抵於抗蝕劑，亦可獲得具有凹凸圖案之抗蝕劑。其次，對晶圓進行蝕刻。此時，與抗蝕劑圖案之凹之部分對應之晶圓表面選擇性地被蝕刻。最後，將抗蝕劑剝離後，獲得具有微細之凹凸圖案之晶圓。 將上述晶圓表面製成具有微細之凹凸圖案之面後，利用水系洗淨液進行表面之洗淨，藉由乾燥等將水系洗淨液去除後，若凹部之寬度較小且凸部之縱橫比較大，則容易產生圖案崩塌。該凹凸圖案係如圖1及圖2般進行定義。圖1係表示對表面製成具有微細之凹凸圖案2之面之晶圓1進行斜視時之模式圖，圖2係表示圖1中之a-a'剖面之一部分者。凹部之寬度5係由如圖2所示般相鄰之凸部3與凸部3之間隔表示，凸部之縱橫比係由將凸部之高度6除以凸部之寬度7所得者表示。洗淨步驟中之圖案崩塌於凹部之寬度為70 nm以下、尤其是45 nm以下且縱橫比為4以上、尤其是6以上之時容易產生。 再者，作為本發明之組合物及表面處理方法之處理對象，並不限於上述構造之晶圓，例如，亦可將三維構造之半導體晶圓作為對象。 (4)關於晶圓之表面處理方法 如上述般藉由蝕刻獲得之於表面具有微細之凹凸圖案之晶圓於本發明之表面處理方法之前，亦可利用水系洗淨液進行洗淨以將蝕刻之殘渣等去除，於該洗淨後亦可將凹部所保持之水系洗淨液置換為與該水系洗淨液不同之洗淨液(以下，記作「洗淨液A」)而進一步進行洗淨。 作為上述水系洗淨液之例，可列舉水、或製成在水中混合有機溶劑、過氧化氫、臭氧、酸、鹼、界面活性劑中之至少1種之水溶液(例如，水之含有率為10質量%以上)者。 又，上述洗淨液A表示有機溶劑、該有機溶劑與水系洗淨液之混合物、於其等中混合有酸、鹼、界面活性劑中之至少1種之洗淨液。 作為於晶圓之凹凸圖案之至少凹部保持上述水系洗淨液或洗淨液A之方式，可列舉以使用旋轉洗淨裝置之洗淨方法為代表之單片方式或使用於洗淨槽內浸漬複數片晶圓而進行洗淨之洗淨裝置之批次方式，該旋轉洗淨裝置一面使晶圓保持大致水平並旋轉一面對旋轉中心附近供給液體而將晶圓逐片洗淨。 作為上述洗淨液A之較佳例之一之有機溶劑之例，可列舉烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、內酯系溶劑、碳酸酯系溶劑、醇類、多元醇之衍生物、含有氮元素之溶劑等。作為醚系溶劑之一種之氫氟醚為無引火點之不燃物，就安全性之觀點而言較佳，其中，九氟-正丁基乙基醚有沸點低於矽烷化劑之傾向，就使用本發明之組合物之蒸氣的置換之操作容易性之觀點而言更佳。 於在凹凸圖案之至少凹部保持有上述水系洗淨液或洗淨液A等液體之狀態下，將本發明之組合物之蒸氣供至上述凹凸圖案表面，於晶圓表面使該蒸氣狀態變化為上述組合物之液體狀態，將上述凹部所保持之液體置換為該組合物之液體並保持，藉此至少於上述凹部表面形成撥水性保護膜。再者，於本發明之晶圓之表面處理方法中，於如上述般供給蒸氣時，上述凹凸圖案之至少凹部所保持之液體較佳為上述洗淨液A，其中，若為非水溶劑，則容易進行使用蒸氣之置換，故而較佳。 作為將本發明之組合物之蒸氣供至上述凹凸圖案表面之方法，例如可列舉於腔室內配置於凹凸圖案之至少凹部保持有上述液體之晶圓，並將另外使組合物蒸發而獲得之蒸氣經由配管或噴嘴供給至凹凸圖案表面之方法等。於蒸氣之供給時，亦可使用氮氣或乾燥空氣等載氣。 又，上述置換後保持之液體狀態之組合物亦可置換為與該組合物不同之洗淨液(以下，記作「洗淨液B」)。 於如上述般利用水系洗淨液或洗淨液A進行洗淨後，使用蒸氣將該洗淨液置換為本發明之液體狀態之組合物，於凹凸圖案之至少凹部保持有液體狀態之該組合物期間，於該凹凸圖案之至少凹部形成上述保護膜。本發明之保護膜未必要連續地形成，又，未必要均勻地形成，但為了能夠賦予更優異之撥水性，更佳為連續地、又均勻地形成。 圖3表示將組合物之蒸氣9供至保持有洗淨液等液體8之凹部的狀態之模式圖。圖3之模式圖之晶圓係表示圖1之a-a'剖面之一部分者。所供給之蒸氣於凹部狀態變化為液體狀態，該組合物之液體置換原本保持於凹部之液體8，於上述凹部保持液體狀態之組合物。所保持之組合物中之上述矽烷化劑與晶圓表面之矽烷醇基進行反應，具有上述撥水性之官能基之部位被固定於晶圓表面，藉此，於該凹部表面形成撥水性保護膜。 將本發明之組合物蒸氣化之方法並無特別限定。例如可列舉批次式之蒸氣化方法，該批次式之蒸氣化方法係將特定量之液體狀態之組合物導入至氣化室，進行該組合物全量蒸發所需之充分之加熱，於全量蒸發後將該蒸氣送出至配管或噴嘴以供給至上述凹凸圖案表面。又，例如可列舉如日本專利5674851號中記載之連續式之蒸氣化方法，該連續式之蒸氣化方法係於配管之一部分設置小規模之氣化部而將組合物加熱，進行蒸發，並將該蒸氣送出至配管或噴嘴。 再者，蒸氣化之溫度係無引起作為保護膜形成成分之上述矽烷化劑之熱分解之虞之溫度，較佳為控制於該矽烷化劑之沸點附近(保護膜形成成分之沸點＋5℃左右)。 作為較佳之蒸氣處理之條件，例如可列舉如日本專利5254120號中記載之條件，該條件係將如上述般獲得之蒸氣與氮氣或氬氣之類之載氣混合後，將該混合氣體供給至上述凹凸圖案表面。 處理中之基板附近之氣體氛圍溫度即蒸氣之溫度較佳為低於原本保持於凹部之液體之沸點。其原因在於：若氣體氛圍溫度(蒸氣之溫度)為該沸點以上，則有於使用蒸氣充分置換原本保持於凹部之液體前，該液體揮發而該凹凸圖案崩塌之虞。 如上述般形成保護膜後，亦可於將殘留於凹凸圖案之至少凹部之液體狀態之上述組合物置換為後洗淨液B後，移至乾燥步驟。作為該洗淨液B之例，可列舉水系洗淨液、有機溶劑、水系洗淨液與有機溶劑之混合物、或於其等中混合有酸、鹼、界面活性劑中之至少1種者、以及其等與上述組合物之混合物等。關於上述洗淨液B，就粒子或金屬雜質之去除之觀點而言，更佳為水、有機溶劑、或水與有機溶劑之混合物。 關於洗淨液B之供給，可為以液體之形式供給該洗淨液之方法，亦可為以蒸氣之形式供給該洗淨液之方法。 作為上述洗淨液B之較佳例之一之有機溶劑之例，可列舉烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、內酯系溶劑、碳酸酯系溶劑、醇類、多元醇之衍生物、含有氮元素之溶劑等。其中，為了價廉地獲得粒子或金屬雜質較少之品質者，較佳為異丙醇。 又，關於上述保護膜，若使用有機溶劑作為上述洗淨液B，則存在由於該洗淨液B之洗淨而撥水性不易下降之情形。 於圖4中表示於藉由本發明之組合物而撥水化之凹部4保持有液體之情形時之模式圖。圖4之模式圖之晶圓係表示圖1之a-a'剖面之一部分者。凹凸圖案表面利用上述組合物形成保護膜11而撥水化。而且，該保護膜11於將液體10自凹凸圖案去除時亦保持於晶圓表面。 於晶圓之凹凸圖案之至少凹部表面，利用本發明之組合物形成保護膜11時，若假設於該表面保持有水時之接觸角為70～130º，則不易產生圖案崩塌，故而較佳。若接觸角較大，則撥水性優異，因此，進而較佳為75～130º，尤佳為80～130º。又，於利用洗淨液B之洗淨之前後，上述接觸角之減小量(洗淨液B之洗淨前之接觸角－洗淨液B之洗淨後之接觸角)較佳為10º以下。 其次，將利用上述組合物形成有保護膜之凹部4所保持之液體藉由乾燥而自凹凸圖案去除。此時，凹部所保持之液體亦可為液體狀態之上述組合物、上述洗淨液B、或其等之混合液。上述混合液係以濃度低於該組合物之方式含有組合物中包含之各成分(矽烷化劑或酸)而成者，該混合液可為將液體狀態之上述組合物置換為洗淨液B之中途狀態之液，亦可為預先將上述各成分混合於洗淨液B而獲得之混合液。就晶圓之潔淨度之觀點而言，較佳為水、有機溶劑、或水與有機溶劑之混合物。又，亦可自上述凹凸圖案表面將液體暫時去除後，於上述凹凸圖案表面保持洗淨液B，其後，進行乾燥。 再者，於在保護膜形成後利用洗淨液B進行洗淨之情形時，該洗淨之時間、即保持洗淨液B之時間就上述凹凸圖案表面之粒子或金屬雜質之去除之觀點而言，較佳為進行10秒鐘以上，更佳為20秒鐘以上。就形成於上述凹凸圖案表面之保護膜之撥水性能之維持效果之觀點而言，若使用有機溶劑作為洗淨液B，則即便進行該洗淨亦有容易維持晶圓表面之撥水性之傾向。另一方面，若上述洗淨之時間變得過長，則生產性變差，故而較佳為15分鐘以內。 藉由上述乾燥，將凹凸圖案所保持之液體去除。該乾燥較佳為藉由旋轉乾燥法、IPA(2-丙醇)蒸氣乾燥、馬蘭葛尼乾燥、加熱乾燥、熱風乾燥、送風乾燥、真空乾燥等周知之乾燥方法而進行。 上述乾燥之後，亦可進而將保護膜11去除。於將撥水性保護膜去除之情形時，將該撥水性保護膜中之C-C鍵、C-F鍵切斷較為有效。作為其方法，只要為能夠將上述鍵切斷者，則並無特別限定，例如可列舉對晶圓表面進行光照射、將晶圓加熱、對晶圓進行臭氧暴露、對晶圓表面進行電漿照射、對晶圓表面進行電暈放電等。 於藉由光照射將保護膜11去除之情形時，較佳為照射相當於該保護膜11中之C-C鍵、C-F鍵之鍵結能量即83 kcal/mol、116 kcal/mol之能量的包含短於340 nm、240 nm之波長的紫外線。作為該光源，使用金屬鹵素燈、低壓水銀燈、高壓水銀燈、準分子燈、碳弧等。關於紫外線照射強度，若為金屬鹵素燈，則較佳為例如以照度計(Konica Minolta Sensing製造之照射強度計UM-10，受光部UM-360[峰感度波長：365 nm，測定波長範圍：310～400 nm])之測定值計為100 mW/cm2 以上，尤佳為200 mW/cm2 以上。再者，若照射強度未達100 mW/cm2 ，則將保護膜11去除需要長時間。又，若為低壓水銀燈，則照射更短波長之紫外線，因此，即便照射強度較低，亦能夠以短時間將保護膜11去除，故而較佳。 又，於藉由光照射將保護膜11去除之情形時，利用紫外線使保護膜11之構成成分分解，同時使臭氧產生，若藉由該臭氧使保護膜11之構成成分氧化揮發，則處理時間變短，故而尤佳。作為該光源，使用低壓水銀燈或準分子燈等。又，亦可一面進行光照射一面將晶圓加熱。 於將晶圓加熱之情形時，較佳為於400～1000℃、較佳為500～900℃下進行晶圓之加熱。該加熱時間較佳為藉由10秒～60分鐘、較佳為30秒～10分鐘之保持而進行。又，於該步驟中，亦可併用臭氧暴露、電漿照射、電暈放電等。又，亦可一面將晶圓加熱一面進行光照射。 藉由加熱將保護膜11去除之方法有使晶圓接觸熱源之方法、於熱處理爐等經加熱之氣體氛圍中放置晶圓之方法等。再者，於經加熱之氣體氛圍中放置晶圓之方法於對複數片晶圓進行處理之情形時，亦容易對晶圓表面均質地賦予用以將保護膜11去除之能量，因此，為操作簡便、處理於短時間內完成而處理能力較高之工業上有利之方法。 於對晶圓進行臭氧暴露之情形時，較佳為將藉由利用低壓水銀燈等之紫外線照射或利用高電壓之低溫放電等產生之臭氧供至晶圓表面。一面對晶圓進行臭氧暴露一面可進行光照射，亦可進行加熱。 藉由將上述光照射、加熱、臭氧暴露、電漿照射、電暈放電組合，而能夠有效率地將晶圓表面之保護膜去除。 [實施例] 以下，表示更具體地揭示本發明之實施形態之實驗例。再者，本發明並不僅限於該等實驗例。 將晶圓之表面製成具有凹凸圖案之面、利用其他洗淨液置換凹凸圖案之至少凹部所保持之洗淨液係於其他文獻等中經過各種研究而已經確立之技術，因此，於本發明中，對組合物之穩定性及利用該組合物之蒸氣對晶圓進行表面處理時之撥水性賦予效果評價進行。再者，於實驗例中，作為於對接觸角進行評價時與晶圓表面接觸之液體，使用作為水系洗淨液之代表之水。 但，於在表面具有凹凸圖案之晶圓之情形時，無法準確評價形成於該凹凸圖案表面之上述保護膜11本身之接觸角。 水滴之接觸角之評價如JIS R 3257「基板玻璃表面之潤濕性試驗方法」中所揭示般，藉由於樣品(基材)表面滴加數μl之水滴，測定水滴與基材表面所成之角度而進行。但，於具有圖案之晶圓之情形時，接觸角變得非常大。其原因在於：因產生Wenzel效果或Cassie效果，故而接觸角受到基材之表面形狀(粗糙度)之影響，表觀上之水滴之接觸角增大。 因此，於本實驗例中，將上述組合物之蒸氣供至表面平滑之晶圓，於晶圓表面形成保護膜，將該保護膜視作形成於在表面形成有凹凸圖案之晶圓之表面之保護膜，進行各種評價。再者，於本實驗例中，作為表面平滑之晶圓，使用於表面平滑之矽晶圓上具有SiO2 層之「附SiO2 膜之晶圓」。 以下敍述詳情。以下，記載評價方法、組合物之製備、使用組合物之蒸氣的晶圓之表面處理方法、評價結果。 [評價方法] (A)組合物之穩定性評價 將組合物之原料混合後，觀察於25℃下靜置6小時後之組合物之外觀，將無不溶物之析出或沈澱之生成者設為合格。又，亦觀察上述混合後靜置4天後之組合物之外觀，對更長時間下之穩定性亦進行評價。 (B)形成於晶圓表面之保護膜之接觸角評價(撥水性賦予效果之評價) 於形成有保護膜之晶圓表面上放置純水約2 μl，利用接觸角計(協和界面科學製造：CA-X型)測定水滴與晶圓表面所成之角(接觸角)，將70º以上設為合格。 [實驗例1] (1)組合物之製備 如表1所示般，作為組合物之原料，將作為矽烷化劑之三甲基矽烷基二甲基胺[(CH3 )3 Si-N(CH3 )2 ](沸點約86℃，以下存在稱作「TMSDMA」之情形)5.0 g、作為溶劑之九氟-正丁基乙基醚[C4 F9 -O-C2 H5 ](沸點約76℃，3M製造之Novec7200)95.0 g混合，而獲得溶液狀態之組合物。即，獲得如表2所示之組成比之組合物。該組合物於混合後，於25℃下靜置6小時及靜置4天後，亦無不溶物之析出或沈澱之生成，顯示出良好之穩定性。 (2)矽晶圓之洗淨 將附平滑熱氧化膜之矽晶圓(於表面具有厚度1 μm之熱氧化膜層之Si晶圓)於1質量%之氫氟酸水溶液中於室溫下浸漬10分鐘，於純水中於室溫下浸漬1分鐘，於2-丙醇(iPA)中於室溫下浸漬1分鐘。 (3)利用蒸氣對矽晶圓表面進行之表面處理 於上述洗淨後，將矽晶圓以溢液有iPA之狀態水平配置於蒸氣處理室，將上述所製備之溶液狀態之組合物藉由下述方法蒸氣化並將該蒸氣供給至蒸氣處理室。然後，於60℃以下之晶圓表面使蒸氣狀態變化為上述組合物之液體狀態，將原本保持於晶圓表面之iPA置換為該組合物之液體。其後，將矽晶圓自蒸氣處理室取出，於iPA中於室溫下浸漬1分鐘，於純水中於室溫下浸漬1分鐘。最後，將矽晶圓自純水中取出，吹送空氣，將表面之純水去除。 上述組合物之蒸氣之供給係以下述方式進行。於加熱至90℃(TMSDMA之沸點86℃＋4℃，無TMSDMA之熱分解之虞之溫度)之蒸氣化室中，一面以2 dm3 /分鐘之流量流通氮氣一面以0.01 g/秒之滴加速度滴加上述製備之溶液狀態之組合物，立即將滴加全量經蒸氣化而得之該組合物蒸氣以氮氣流供給至蒸氣處理室。將該處理進行60秒鐘。 以上述(B)中記載之要點對接觸角進行評價，結果，如表3所示，表面處理前之初始接觸角未達10º者之表面處理後之接觸角成為84º，顯示出撥水性賦予效果。 [表1] [表2] [表3] [實驗例2～7、比較實驗例1～22] 作為組合物之原料，變更實驗例1所使用之矽烷化劑之種類、含氟醚於溶劑中之含量、其他溶劑之種類或含量、酸之種類或濃度、蒸氣化室之溫度等條件，除此以外，與實驗例1同樣地進行晶圓之表面處理，進而進行其評價。將原料、組合物、及評價結果表示於表1～6。再者，於表中，「TMSDEA」係指三甲基矽烷基二乙基胺，「TFAA」係指三氟乙酸酐，「HMDS」係指1,1,1,3,3,3-六甲基二矽氮烷，「TMSTFA」係指三氟乙酸三甲基矽烷酯，「TFA」係指三氟乙酸，「TMDS」係指1,1,3,3-四甲基二矽氮烷，「PGMEA」係指丙二醇單甲醚乙酸酯，「DCTFP」係指1,2-二氯-3,3,3-三氟丙烯。 再者，於實驗例2中，將組合物原料混合後，TMSDMA與TFAA進行反應，作為原料之酸化合物之TFAA被反應消耗，而獲得含有作為酸之TMSTFA、作為副產物之N,N-二甲基-2,2,2-三氟乙醯胺(以下，DMTFAA)、及多餘之TMSDMA之表2所示之組合物。 又，於比較實驗例11中，將組合物原料混合後，HMDS與TFA進行反應，作為原料之酸化合物之TFA被反應消耗，而獲得含有作為酸之TMSTFA、作為副產物之NH3 、及多餘之HMDS之表2所示之組合物。 又，於比較實驗例12中，將組合物原料混合後，HMDS與TFAA進行反應，作為原料之酸化合物之TFAA被反應消耗，而獲得含有作為酸之TMSTFA、作為副產物之三甲基矽烷基三氟乙醯胺(以下，TMSTFAA)、及多餘之HMDS之表2所示之組合物。 又，於比較實驗例15中，將組合物原料混合後，TMDS與TFA進行反應，作為原料之酸化合物之TFA被反應消耗，而獲得含有作為酸之DMSTFA、作為副產物之NH3 、及多餘之TMDS之表2所示之組合物。 又，於比較實驗例16中，將組合物原料混合後，TMDS與TFAA進行反應，作為原料之酸化合物之TFAA被反應消耗，而獲得含有作為酸之DMSTFA、作為副產物之二甲基矽烷基三氟乙醯胺(以下，DMSTFAA)、及多餘之TMDS之表2所示之組合物。 又，於比較實驗例18中，將組合物原料混合後，HMDS與TFA進行反應，作為原料之酸化合物之TFA被反應消耗，而獲得含有作為酸之TMSTFA、作為副產物之NH3 、及多餘之HMDS之表5所示之組合物。 又，於比較實驗例19中，將組合物原料混合後，HMDS與TFAA進行反應，作為原料之酸化合物之TFAA被反應消耗，而獲得含有作為酸之TMSTFA、作為副產物之TMSTFAA、及多餘之HMDS之表5所示之組合物。 又，於比較實驗例22中，將組合物原料混合後，TMDS與TFA進行反應，作為原料之酸化合物之TFA被反應消耗，而獲得含有作為酸之DMSTFA、作為副產物之NH3 、及多餘之TMDS之表5所示之組合物。 [表4] [表5] [表6] 本發明中規定之組合物均係使用沸點低於上述矽烷化劑之沸點之上述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑者，因此，能夠於無引起矽烷化劑之熱分解之虞之溫度下蒸氣化，於將原料混合後於25℃下靜置6小時後未觀察到不溶物之析出或沈澱之生成而顯示出優異之穩定性。其中，關於組合物由矽烷化劑及含氟醚所構成之實驗例1及7、及組合物由矽烷化劑、含氟醚及酸所構成之實驗例2，於將原料混合後於25℃下靜置4天後，亦未觀察到不溶物之析出或沈澱之生成，而顯示出尤其優異之穩定性。又，使用本發明中規定之組合物之實驗例1～7均顯示出良好之撥水性賦予效果。 另一方面，於使用偏離本發明之規定之組合物之比較實驗例1～16中，組合物之穩定性不充分(於該情形時，不進行接觸角之評價)、或撥水性賦予效果不充分。 關於比較實驗例17～22，除使矽烷化劑濃度對照上述實驗例設為約5.0質量%以外，為相當於專利文獻1(日本專利第5648053號公報)之實施例1～6之實驗例，雖顯示出與本案之實驗例同等之撥水性賦予效果，但組合物之穩定性不充分。又，因含有3質量%之沸點高於保護膜形成成分之沸點之溶劑，故將蒸氣化時之溫度設為較矽烷化劑之沸點高20℃以上之溫度，因此有引起矽烷化劑之熱分解之虞。(1) Composition according to the present invention The composition of the present invention is in a state in which a wafer having a concave-convex pattern on a surface and at least a wafer having a Si element in the concave portion is maintained in a liquid state in at least a concave portion of the concave-convex pattern Then, the surface of the concave-convex pattern is supplied as a vapor, and the surface of the wafer is changed from a vapor state to a liquid state, and the liquid originally held in the concave portion is replaced. Further, by the replacement, the composition in a liquid state is held in the concave portion, whereby a water-repellent protective film is formed on the surface of the concave portion. The composition of the present invention comprises: a decylating agent represented by the following formula [1]; and a fluorinated ether represented by the following formula [2] having a boiling point lower than the boiling point of the above sulfonating agent in a total amount of 100% by mass Among the %, the solvent is from 99.8 to 100% by mass, and the amount of the decylating agent is from 2 to 30% by mass based on the total amount of the above alkylating agent and solvent.[In the formula [1], R1 Independently from each other, it is a group selected from a hydrocarbon group having a carbon number of 1 to 10 and a hydrocarbon group having a carbon number of 1 to 8 partially or wholly substituted with a fluorine element, R2 Independently of each other, it is a group selected from a methyl group, an ethyl group, or an ethyl group which is partially or wholly substituted with a fluorine element. x is an integer from 1 to 3, y is an integer from 1 to 3, and 4-x-y is an integer from 0 to 2],[in the formula [2], Cn F2n + 1 a linear perfluoroalkyl group having a carbon number of n=4 to 5, Cm H2m + 1 A linear or branched alkyl group having a carbon number of m = 2 to 6]. In the decylating agent represented by the above formula [1], (R1 )y (H)4 - x - y The Si system has a site of a water-repellent functional group. Further, the above-described decylating agent reacts with a stanol group on the surface of the wafer, and the portion having the water-repellent functional group is fixed to the surface of the wafer, whereby a water-repellent protective film is formed on the surface of the wafer. When the composition further contains an acid, the above-mentioned decylating agent reacts rapidly with the surface of the wafer by the acid, and the water repellency imparting effect is easily obtained. Specific examples of the above sulfonating agent include (CH)3 )3 SiN (CH3 )2 , C2 H5 Si(CH3 )2 N (CH3 )2 (C2 H5 )2 Si(CH3 )N(CH)3 )2 (C2 H5 )3 SiN (CH3 )2 , C3 H7 Si(CH3 )2 N (CH3 )2 (C3 H7 )2 Si(CH3 )N(CH)3 )2 (C3 H7 )3 SiN (CH3 )2 , C4 H9 Si(CH3 )2 N (CH3 )2 (C4 H9 )3 SiN (CH3 )2 , C5 H11 Si(CH3 )2 N (CH3 )2 , C6 H13 Si(CH3 )2 N (CH3 )2 , C7 H15 Si(CH3 )2 N (CH3 )2 , C8 H17 Si(CH3 )2 N (CH3 )2 , C9 H19 Si(CH3 )2 N (CH3 )2 , C10 Htwenty one Si(CH3 )2 N (CH3 )2 , C11 Htwenty three Si(CH3 )2 N (CH3 )2 , C12 H25 Si(CH3 )2 N (CH3 )2 , C13 H27 Si(CH3 )2 N (CH3 )2 , C14 H29 Si(CH3 )2 N (CH3 )2 , C15 H31 Si(CH3 )2 N (CH3 )2 , C16 H33 Si(CH3 )2 N (CH3 )2 , C17 H35 Si(CH3 )2 N (CH3 )2 , C18 H37 Si(CH3 )2 N (CH3 )2 , (CH3 )2 Si(H)N(CH3 )2 , CH3 Si(H)2 N (CH3 )2 (C2 H5 )2 Si(H)N(CH3 )2 , C2 H5 Si(H)2 N (CH3 )2 , C2 H5 Si(CH3 )(H)N(CH)3 )2 (C3 H7 )2 Si(H)N(CH3 )2 , C3 H7 Si(H)2 N (CH3 )2 , CF3 CH2 CH2 Si(N(CH)3 )2 )3 , C2 F5 CH2 CH2 Si(N(CH)3 )2 )3 , C3 F7 CH2 CH2 Si(N(CH)3 )2 )3 , C4 F9 CH2 CH2 Si(N(CH)3 )2 )3 , C5 F11 CH2 CH2 Si(N(CH)3 )2 )3 , C6 F13 CH2 CH2 Si(N(CH)3 )2 )3 , C7 F15 CH2 CH2 Si(N(CH)3 )2 )3 , C8 F17 CH2 CH2 Si(N(CH)3 )2 )3 , CF3 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C2 F5 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C3 F7 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C4 F9 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C5 F11 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C6 F13 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C7 F15 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , C8 F17 CH2 CH2 Si(CH3 )(N(CH)3 )2 )2 , CF3 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C2 F5 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C3 F7 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C4 F9 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C5 F11 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C6 F13 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C7 F15 CH2 CH2 Si(CH3 )2 N (CH3 )2 , C8 F17 CH2 CH2 Si(CH3 )2 N (CH3 )2 , CF3 CH2 CH2 Si(CH3 )(H)N(CH)3 )2 Or the dimethylamino group of the above dimethylamino decane (-N(CH)3 )2 Base) is -N(C2 H5 )2 , -N(CH3 )C(O)CH3 , -N(CH3 )C(O)CF3 Compounds and the like. Among them, at least one selected from the group consisting of trimethyldecyldimethylamine and trimethyldecyldiethylamine is more excellent in the water-repellent imparting effect. Among the above decylating agents, the above-mentioned formula [1] -N(R2 )2 The base represented is -N(CH3 )2 Base or -N(C2 H5 )2 The base is particularly fast in response to the surface of the wafer and is therefore preferred. The solvent contained in the above composition contains, in a total amount of 100% by mass, a fluorine-containing ether represented by the above formula [2] having a boiling point lower than the boiling point of the above-described decylating agent of 99.8 to 100% by mass. When a large amount (more than 0.2% by mass) of the composition contains a solvent having a boiling point equal to or higher than the boiling point of the above-described decylating agent, there is a possibility of causing thermal decomposition of the alkylating agent upon vaporization. As described above, the reason is that the thermal decomposition is caused by excessive temperature or heat applied to the decylating agent before the entire amount of the composition is vaporized (until the total amount of the high-boiling solvent is evaporated). Further, by using the above-described specific alkylating agent and solvent, the composition of the vaporization before the vaporization is difficult to decompose (the stability of the composition is high), and it is difficult to precipitate or precipitate the insoluble matter. produce. The solvent contained in the above composition is further preferably only the above-mentioned fluorine-containing ether from the viewpoint that it is difficult to cause precipitation or precipitation of insoluble matter. As the fluorine-containing ether, from the viewpoint of occurrence of precipitation or precipitation of insoluble matter, a nonafluoro-n-butyl ethyl ether is preferably exemplified. Of course, as a combination of the alkylating agent and the fluorine-containing ether contained in the above composition, a combination of a boiling point of the fluorine-containing ether and a boiling point of the alkylating agent is selected. Further, in the decylating agent and the fluorinated ether contained in the composition, when the difference between the boiling points of the two is within 20 ° C, the two components are likely to boil and evaporate at the same time, which is particularly preferable. The solvent contained in the above composition may contain a solvent other than the above-mentioned fluorine-containing ether (hereinafter, abbreviated as "other solvent"). Specific examples of the other solvent include a fluorine-containing ether which does not satisfy the above formula [2] (for example, nonafluoro-n-butyl methyl ether [C]4 F9 -O-CH3 ] (boiling point about 61 ° C, Novec 7100 manufactured by 3M), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl) -pentane [C2 F5 CF (OCH3 )CF(CF3 )2 (Boiling point: about 98 ° C, Novec 7300, manufactured by 3M, etc.) or cyclohexane. The amount of the alkylating agent is 2 to 30% by mass based on the total amount of the above-mentioned alkylating agent and solvent (hereinafter, abbreviated as "the concentration of the alkylating agent"). When it is 2% by mass or more, the water repellency imparting effect can be exhibited. In addition, when it is 30% by mass or less, it is possible to suppress the influence on the resin member or the like of the cleaning device. When it is 3% by mass or more, it is easy to exhibit a more excellent water-repellent imparting effect, which is preferable. In addition, when it is 20% by mass or less, the influence on the resin member or the like of the cleaning device is further reduced, and the price can be suppressed, which is preferable. The concentration is further preferably from 5 to 10% by mass. Moreover, when the composition is composed of the above-described decylating agent and the above-mentioned fluorine-containing ether, it is easy to vaporize all the components in the composition, and it is possible to suppress deterioration due to the reaction of the alkylating agent in the composition, and it is possible to improve the composition. The ignition point of the composition is preferred. Alternatively, the above composition may further comprise an acid. As described above, the above-described decylating agent reacts rapidly with the surface of the wafer by an acid, and the water repellency imparting effect is easily obtained. Specific examples of the acid include trimethyl decyl trifluoroacetate, trimethyl decyl trifluoromethanesulfonate, dimethyl decyl trifluoroacetate, dimethyl decyl trifluoromethanesulfonate, and the like. Butyl dimethyl decyl fluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, hexyl dimethyl decyl trifluoromethanesulfonate, octyl trifluoroacetate Dimethyl decyl ester, octyl dimethyl decyl trifluoromethanesulfonate, decyl dimethyl decyl trifluoroacetate, decyl dimethyl decyl trifluoromethanesulfonate, and the like. Among the above acids, trimethyl decyl trifluoroacetate is preferred because of its excellent storage stability. In the case where the above composition further contains an acid, the amount of the acid is preferably 0.01 to 30% by mass based on the total amount of the above-described alkylating agent, solvent and acid (hereinafter, abbreviated as "acid concentration"). The concentration is more preferably 0.05 to 20% by mass from the viewpoint of the water-repellent imparting effect. The acid may be produced by reacting the above sulfonating agent with an acid compound. For example, when trimethyl decyl dimethylamine as a decylating agent and trifluoroacetic anhydride as an acid compound are used as a raw material of the composition, the two are reacted in a solvent to form trimethyl trifluoroacetate. A decyl ester that functions as an acid in the composition. Further, in the case of using an acid formed by the reaction, it is important that the acid compound as a raw material (trifluoroacetic anhydride in the above case) is excessively charged as a raw material of a decylating agent (in the above) In the case of trimethyldecyl dimethylamine). In the composition obtained as a result of the above reaction, the amount of the alkylating agent is added in an amount of 2 to 30% by mass based on the total amount of the above-mentioned alkylating agent and solvent. Examples of the acid compound include trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride, and particularly preferably trifluoroacetic anhydride. The composition of the present invention may also contain an additive such as an antioxidant to further improve the stability. For example, 4-methoxyphenol, dibutylhydroxytoluene, butylhydroxyanisole, 1,4-benzenediol, 2-(1,1-dimethylethyl)-1,4 - benzenediol, 1,4-benzoquinone, 1-octyl thiol, 1-anthracene thiol, 1-anthracene thiol, 1-undecan thiol, 1-dodecane thiol, octyl-3 , 5-di-t-butyl-4-hydroxy-hydrocinnamic acid (for example, Irganox 1135 manufactured by BASF), 6-t-butyl-2,4-xylenol, and the like. Further, in view of the cleanliness of the composition, the above additive is preferably a liquid, and is preferably, for example, a 1-dodecanethiol or an octyl-3,5-di-dimer which is liquid at 25 ° C at atmospheric pressure. Tributyl-4-hydroxy-hydrocinnamic acid (for example, Irganox 1135 manufactured by BASF), 6-t-butyl-2,4-xylenol, and the like. Further, the total amount of water in the starting material of the above composition is preferably 2,000 ppm by mass or less based on the total amount of the raw material. When the total amount of the water exceeds 2000 ppm by mass, the effect of the above-mentioned decylating agent is lowered (the effect of the acid is also lowered when the acid is contained), and it is not easy to form the protective film in a short time. Therefore, the total amount of the water component in the raw material of the composition is preferably as small as possible, and is preferably 500 ppm by mass or less, and more preferably 200 ppm by mass or less. Further, when the amount of water is large, the storage stability of the composition is likely to be lowered. Therefore, the amount of water is preferably small, preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less. Further, the smaller the amount of the water, the more preferable, but the amount of water in the raw material of the composition may be 0.1 ppm by mass or more as long as it is within the above content range. Therefore, the decylating agent or solvent contained in the above composition is preferably one which does not contain a large amount of water. Further, in the above composition, in the measurement of the particles in the liquid phase by the light scattering type liquid particle detector, the number of particles larger than 0.2 μm is preferably 100 or less per 1 mL of the composition. When the number of the particles larger than 0.2 μm is more than 100 per 1 mL of the composition, there is a possibility that the pattern is damaged by the particles, which is a cause of a decrease in the yield of the device and a decrease in reliability, which is not preferable. Further, the inside of the steam treatment device may be contaminated, and the yield of the device is further lowered and the reliability is further lowered. Further, when the number of particles larger than 0.2 μm is 100 or less per 1 mL of the composition, the surface of the wafer (protective film surface) washed with a solvent or water after forming the protective film can be omitted or reduced. Clean, so better. Further, the smaller the number of particles larger than 0.2 μm, the more preferable, but the composition may be one or more per 1 mL as long as it is within the above content range. Further, in the composition of the present invention, the particle measurement in the liquid phase is measured by a commercially available measurement device in a light scattering liquid particle measurement method using a laser as a light source, and the particle size is referred to as a particle size. Light scattering equivalent diameter of PSL (polystyrene latex) standard particle reference. Here, the above-mentioned particles refer to dust, arsenic, and organic solid matter which are contained in the form of impurities in the form of impurities in the form of impurities, such as dust, arsenic, organic solids, inorganic solids, and the like contained in the raw material. Particles such as inorganic solids and the like are those which are not dissolved in the composition and are present in the form of particles. Further, the content of each element (metal impurity) of Na, Mg, K, Ca, Mn, Fe, Cu, Li, Al, Cr, Ni, Zn and Ag in the above composition is preferably relative to the total amount of the composition. It is 0.1 mass ppb or less each. When the content of the metal impurities exceeds 0.1 mass ppb based on the total amount of the composition, the junction leakage current of the device is increased, which is a cause of a decrease in the yield of the device and a decrease in reliability, which is not preferable. Further, the inside of the steam treatment device may be contaminated, and the yield of the device is further lowered and the reliability is further lowered. Further, when the content of the metal impurities is 0.1 mass ppb or less per the total amount of the composition, the surface of the wafer (the surface of the protective film) which is formed by using a solvent or water after the protective film is formed on the surface of the wafer can be omitted or reduced. It is better to wash it. Therefore, the content of the metal impurities is preferably as small as possible. However, as long as it is within the above content range, each element may be 0.001 mass ppb or more based on the total amount of the composition. (2) Water-repellent protective film In the present invention, the water-repellent protective film refers to a film which is formed on the surface of the wafer to reduce the wettability of the surface of the wafer, that is, a film which imparts water repellency. In the present invention, water repellency means that the surface energy of the surface of the article is lowered, and the interaction between water or other liquid and the surface (interface) of the article, such as hydrogen bonding, intermolecular force, and the like, is reduced. In particular, the effect of reducing the interaction with water is large, but the effect of reducing the interaction is also obtained for a liquid mixture other than water or water or a liquid other than water. By this reduction in interaction, the contact angle of the liquid relative to the surface of the article can be increased. Further, the water-repellent protective film may be formed of the above-described decylating agent, or may be a reactant containing a decylating agent as a main component. (3) The wafer as the wafer includes at least a part of a surface of the wafer on which a film containing Si element such as tantalum, niobium oxide or tantalum nitride is formed or when the uneven pattern is formed. Those containing Si element such as ruthenium, osmium oxide, or tantalum nitride. Further, the surface on which the Si element is contained in the uneven pattern can be formed from the composition. In general, in order to obtain a wafer having a fine concavo-convex pattern on the surface, first, after applying a resist on the surface of the smoothed wafer, the resist is exposed through the resist mask to expose the exposed resist. The etchant or the unexposed resist is etched away, whereby a resist having a desired concavo-convex pattern is formed. Further, by pressing the patterned mold against the resist, a resist having a concavo-convex pattern can also be obtained. Next, the wafer is etched. At this time, the wafer surface corresponding to the concave portion of the resist pattern is selectively etched. Finally, after the resist is peeled off, a wafer having a fine concavo-convex pattern is obtained. After the surface of the wafer is formed into a surface having a fine concavo-convex pattern, the surface is washed with a water-based cleaning solution, and after the aqueous cleaning solution is removed by drying or the like, the width of the concave portion is small and the convex portion is vertically and horizontally Larger, it is prone to pattern collapse. This concave-convex pattern is defined as shown in FIGS. 1 and 2 . Fig. 1 is a schematic view showing a state in which the wafer 1 having a surface having a fine uneven pattern 2 is squinted, and Fig. 2 is a view showing a portion of the a-a' cross section of Fig. 1. The width 5 of the concave portion is represented by the interval between the convex portion 3 and the convex portion 3 adjacent to each other as shown in Fig. 2. The aspect ratio of the convex portion is represented by dividing the height 6 of the convex portion by the width 7 of the convex portion. The pattern in the washing step collapses when the width of the concave portion is 70 nm or less, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more. Further, the processing target of the composition and the surface treatment method of the present invention is not limited to the wafer having the above structure, and for example, a semiconductor wafer having a three-dimensional structure may be targeted. (4) Surface Treatment Method of Wafer A wafer having a fine concavo-convex pattern on the surface obtained by etching as described above may be washed with an aqueous cleaning solution to be etched before the surface treatment method of the present invention. After the cleaning, the water-based cleaning liquid held in the concave portion may be replaced with a cleaning liquid different from the aqueous cleaning liquid (hereinafter referred to as "cleaning liquid A"), and further washed. net. Examples of the water-based cleaning liquid include water or an aqueous solution in which at least one of an organic solvent, hydrogen peroxide, ozone, an acid, a base, and a surfactant is mixed in water (for example, a water content ratio) 10% by mass or more). In addition, the cleaning liquid A is an organic solvent, a mixture of the organic solvent and the aqueous cleaning solution, and at least one of an acid, a base, and a surfactant mixed with the cleaning liquid. The manner in which the water-based cleaning liquid or the cleaning liquid A is held in at least the concave portion of the concave-convex pattern of the wafer is exemplified by a single-piece method represented by a cleaning method using a rotary cleaning device or impregnation in a cleaning tank. A batch method of cleaning a plurality of wafers to clean the wafer while maintaining the wafer substantially horizontally and rotating to supply liquid near the center of rotation to wash the wafer piece by piece. Examples of the organic solvent which is one of preferable examples of the cleaning solution A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfonium-based solvents, lactone-based solvents, and carbonate-based solvents. , alcohols, derivatives of polyols, solvents containing nitrogen, and the like. The hydrofluoroether which is one of the ether solvents is a non-combustible material having no ignition point, and is preferable from the viewpoint of safety, wherein the nonafluoro-n-butyl ethyl ether has a tendency to have a lower boiling point than the alkylating agent. It is more preferable from the viewpoint of ease of handling of the replacement of the vapor of the composition of the present invention. The vapor of the composition of the present invention is supplied to the surface of the concave-convex pattern in a state where the liquid such as the aqueous cleaning liquid or the cleaning liquid A is held in at least the concave portion of the concave-convex pattern, and the vapor state is changed to the surface of the wafer. In the liquid state of the composition, the liquid held by the concave portion is replaced with a liquid of the composition and held, whereby a water-repellent protective film is formed on at least the surface of the concave portion. Further, in the surface treatment method of the wafer of the present invention, when the vapor is supplied as described above, the liquid held by at least the concave portion of the concave-convex pattern is preferably the cleaning liquid A, and if it is a non-aqueous solvent, It is preferable to use a vapor replacement. The method of supplying the vapor of the composition of the present invention to the surface of the uneven pattern is, for example, a vapor which is disposed in a cavity in which at least a concave portion of the concave-convex pattern holds the liquid, and which is obtained by evaporating the composition. A method of supplying to a surface of a concave-convex pattern via a pipe or a nozzle. For the supply of steam, a carrier gas such as nitrogen or dry air may also be used. Further, the composition in a liquid state held after the replacement may be replaced with a washing liquid (hereinafter referred to as "cleaning liquid B") different from the composition. After washing with the aqueous cleaning solution or the cleaning solution A as described above, the cleaning liquid is replaced with the composition in the liquid state of the present invention by using the vapor, and the combination of the liquid state is maintained in at least the concave portion of the concave-convex pattern. During the object period, the protective film is formed on at least the concave portion of the concave-convex pattern. The protective film of the present invention is not necessarily formed continuously, and it is not necessary to form it uniformly. However, in order to impart more excellent water repellency, it is more preferably continuously and uniformly formed. Fig. 3 is a schematic view showing a state in which the vapor 9 of the composition is supplied to a recess in which the liquid 8 such as a cleaning liquid is held. The wafer of the schematic diagram of Fig. 3 represents one of the a-a' sections of Fig. 1. The supplied vapor changes to a liquid state in the state of the concave portion, and the liquid of the composition is replaced with the liquid 8 originally held in the concave portion, and the composition is maintained in a liquid state in the concave portion. The decylating agent in the retained composition reacts with a stanol group on the surface of the wafer, and a portion having the above-mentioned water-repellent functional group is fixed on the surface of the wafer, thereby forming a water-repellent protective film on the surface of the concave portion. . The method of vaporizing the composition of the present invention is not particularly limited. For example, a batch type vaporization method may be mentioned. The batch type vaporization method introduces a specific amount of a liquid state composition into a gasification chamber, and performs sufficient heating for the entire amount of evaporation of the composition. After evaporation, the vapor is sent to a pipe or a nozzle to be supplied to the surface of the concave-convex pattern. Further, for example, a continuous vaporization method as described in Japanese Patent No. 5,674, 851, which is a method in which a small-scale gasification portion is provided in one portion of a pipe to heat the composition and evaporate, and This vapor is sent to a pipe or a nozzle. Further, the temperature at which the vaporization is carried out is such that the temperature at which the thermal decomposition of the above-described decylating agent is not formed as a protective film forming component is preferably controlled near the boiling point of the sulfonating agent (the boiling point of the protective film forming component is about +5 ° C). ). As a condition for the preferable steam treatment, for example, a condition as described in Japanese Patent No. 5254120, which is obtained by mixing the vapor obtained as described above with a carrier gas such as nitrogen or argon, is supplied to the mixed gas. The above-mentioned concave and convex pattern surface. The temperature of the gas atmosphere near the substrate in the process, that is, the temperature of the vapor, is preferably lower than the boiling point of the liquid originally held in the recess. The reason for this is that if the gas atmosphere temperature (temperature of the vapor) is equal to or higher than the boiling point, the liquid volatilizes and the uneven pattern collapses before the vapor is sufficiently replaced by the liquid originally held in the concave portion. After the protective film is formed as described above, the composition in a liquid state remaining in at least the concave portion of the concave-convex pattern may be replaced with the post-cleaning liquid B, and then transferred to a drying step. Examples of the cleaning liquid B include a mixture of an aqueous cleaning solution, an organic solvent, an aqueous cleaning solution, and an organic solvent, or at least one of an acid, a base, and a surfactant mixed therein. And a mixture thereof or the like with the above composition. The cleaning liquid B is more preferably water, an organic solvent or a mixture of water and an organic solvent from the viewpoint of removing particles or metal impurities. The supply of the cleaning liquid B may be a method of supplying the cleaning liquid in the form of a liquid, or a method of supplying the cleaning liquid in the form of a vapor. Examples of the organic solvent which is one of preferable examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, anthraquinone-based solvents, lactone-based solvents, and carbonate-based solvents. , alcohols, derivatives of polyols, solvents containing nitrogen, and the like. Among them, isopropyl alcohol is preferred in order to obtain a low quality of particles or metal impurities at low cost. Further, when the organic solvent is used as the cleaning liquid B as the protective film, the water repellency of the cleaning liquid B is not easily lowered. Fig. 4 is a schematic view showing a state in which the recessed portion 4 which is dialed by the composition of the present invention is kept in a liquid state. The wafer of the schematic diagram of Fig. 4 represents one of the a-a' sections of Fig. 1. The surface of the concave-convex pattern is water-repellent by forming the protective film 11 using the above composition. Moreover, the protective film 11 is also held on the surface of the wafer when the liquid 10 is removed from the concave-convex pattern. When the protective film 11 is formed on the surface of at least the concave portion of the concave-convex pattern of the wafer by the composition of the present invention, if the contact angle is 70 to 130° when water is held on the surface, pattern collapse is less likely to occur, which is preferable. When the contact angle is large, the water repellency is excellent. Therefore, it is preferably from 75 to 130o, particularly preferably from 80 to 130o. Further, after the cleaning of the cleaning liquid B, the contact angle is reduced (the contact angle before washing of the cleaning liquid B - the contact angle after washing of the cleaning liquid B) is preferably 10 o. the following. Next, the liquid held by the concave portion 4 in which the protective film is formed by the above composition is removed from the concave-convex pattern by drying. At this time, the liquid held by the concave portion may be a mixture of the above composition in a liquid state, the above-mentioned cleaning liquid B, or the like. The mixed liquid is obtained by containing each component (alkylating agent or acid) contained in the composition at a concentration lower than that of the composition, and the mixed liquid may be prepared by replacing the above composition in a liquid state with the cleaning liquid B. The liquid in the middle may be a mixed liquid obtained by mixing the above components in the cleaning liquid B in advance. From the viewpoint of the cleanliness of the wafer, water, an organic solvent, or a mixture of water and an organic solvent is preferred. Moreover, after the liquid is temporarily removed from the surface of the uneven pattern, the cleaning liquid B is held on the surface of the concave-convex pattern, and then dried. Further, when the cleaning film B is used for cleaning after the formation of the protective film, the cleaning time, that is, the time during which the cleaning liquid B is held, is removed from the viewpoint of the removal of particles or metal impurities on the surface of the uneven pattern. In other words, it is preferably carried out for 10 seconds or longer, more preferably for 20 seconds or longer. From the viewpoint of the effect of maintaining the water repellency of the protective film formed on the surface of the uneven pattern, if an organic solvent is used as the cleaning liquid B, it is easy to maintain the water repellency of the wafer surface even if the cleaning is performed. . On the other hand, if the washing time is too long, the productivity is deteriorated, and therefore it is preferably within 15 minutes. The liquid held by the concave-convex pattern is removed by the above drying. The drying is preferably carried out by a known drying method such as spin drying, IPA (2-propanol) vapor drying, mazonic drying, heat drying, hot air drying, air drying, and vacuum drying. After the above drying, the protective film 11 can be further removed. When the water-repellent protective film is removed, it is effective to cut the C-C bond and the C-F bond in the water-repellent protective film. The method is not particularly limited as long as the bond can be cut, and for example, the surface of the wafer is irradiated with light, the wafer is heated, the wafer is exposed to ozone, and the surface of the wafer is plasma-treated. Irradiation, corona discharge on the surface of the wafer, and the like. In the case where the protective film 11 is removed by light irradiation, it is preferable to irradiate a short amount of energy equivalent to the bonding energy of the CC bond and the CF bond in the protective film 11, that is, 83 kcal/mol or 116 kcal/mol. Ultraviolet light at wavelengths of 340 nm and 240 nm. As the light source, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an excimer lamp, a carbon arc or the like is used. The ultraviolet ray irradiation intensity is preferably an illuminance meter (an illumination intensity meter UM-10 manufactured by Konica Minolta Sensing, light receiving unit UM-360 [peak sensitivity wavelength: 365 nm, measurement wavelength range: 310). The measured value of ~400 nm]) is 100 mW/cm.2 Above, especially 200 mW/cm2 the above. Furthermore, if the irradiation intensity is less than 100 mW/cm2 Then, it takes a long time to remove the protective film 11. Further, in the case of a low-pressure mercury lamp, ultraviolet rays having a shorter wavelength are irradiated. Therefore, even if the irradiation intensity is low, the protective film 11 can be removed in a short time, which is preferable. In the case where the protective film 11 is removed by light irradiation, the constituent components of the protective film 11 are decomposed by ultraviolet rays, and ozone is generated. When the constituent components of the protective film 11 are oxidized and volatilized by the ozone, the processing time is It is shorter, so it is especially good. As the light source, a low pressure mercury lamp, an excimer lamp or the like is used. Further, the wafer may be heated while being irradiated with light. In the case of heating the wafer, it is preferred to heat the wafer at 400 to 1000 ° C, preferably 500 to 900 ° C. The heating time is preferably carried out by holding for 10 seconds to 60 minutes, preferably 30 seconds to 10 minutes. Further, in this step, ozone exposure, plasma irradiation, corona discharge, or the like may be used in combination. Further, it is also possible to perform light irradiation while heating the wafer. The method of removing the protective film 11 by heating includes a method of contacting the wafer with a heat source, a method of placing a wafer in a heated gas atmosphere such as a heat treatment furnace, and the like. Furthermore, in the case of processing a plurality of wafers in a heated gas atmosphere, it is also easy to impart a uniform energy to the surface of the wafer to remove the protective film 11, and therefore, It is a simple and industrially advantageous method for processing in a short period of time with high processing capacity. In the case where the wafer is subjected to ozone exposure, it is preferable to supply ozone to the wafer surface by ultraviolet irradiation using a low-pressure mercury lamp or the like or ozone generated by a high-voltage low-temperature discharge or the like. It can be irradiated with light or exposed to the surface of the wafer for ozone exposure. By combining the above-described light irradiation, heating, ozone exposure, plasma irradiation, and corona discharge, the protective film on the wafer surface can be efficiently removed. [Examples] Hereinafter, experimental examples in which embodiments of the present invention are more specifically disclosed will be described. Furthermore, the invention is not limited to the experimental examples. A technique in which the surface of the wafer is formed into a surface having a concave-convex pattern, and at least the concave portion of the concave-convex pattern is replaced by another cleaning liquid, which has been established in various literatures and the like, has been established by various studies. The evaluation of the water repellency imparting effect when the composition was subjected to surface treatment by the stability of the composition and the vapor of the composition was carried out. In the experimental example, as the liquid which is in contact with the surface of the wafer when the contact angle is evaluated, water which is representative of the aqueous cleaning solution is used. However, in the case of a wafer having a concave-convex pattern on its surface, the contact angle of the protective film 11 itself formed on the surface of the concave-convex pattern cannot be accurately evaluated. Evaluation of the contact angle of water droplets As described in JIS R 3257 "Test method for wettability of substrate glass surface", water droplets and surface of the substrate were measured by dropping a few μl of water droplets on the surface of the sample (substrate). From the angle. However, in the case of a patterned wafer, the contact angle becomes very large. The reason for this is that the contact angle is affected by the surface shape (roughness) of the substrate due to the effect of the Wenzel effect or the Cassie effect, and the contact angle of the apparent water droplet is increased. Therefore, in the present experimental example, the vapor of the above composition is supplied to the wafer having a smooth surface to form a protective film on the surface of the wafer, and the protective film is regarded as being formed on the surface of the wafer on which the concave-convex pattern is formed. The protective film was subjected to various evaluations. Furthermore, in this experimental example, as a surface smooth wafer, it is used on a smooth surface of the wafer with SiO.2 Layer of "with SiO2 Film Wafer". The details are described below. Hereinafter, the evaluation method, the preparation of the composition, the surface treatment method of the wafer using the vapor of the composition, and the evaluation results will be described. [Evaluation method] (A) Evaluation of the stability of the composition After the raw materials of the composition were mixed, the appearance of the composition after standing at 25 ° C for 6 hours was observed, and the generation of the precipitate-free or precipitate-free was set as qualified. Further, the appearance of the composition after standing for 4 days after the mixing was observed, and the stability under a longer period of time was also evaluated. (B) Evaluation of contact angle of protective film formed on the surface of the wafer (evaluation of water-repellent imparting effect) About 2 μl of pure water was placed on the surface of the wafer on which the protective film was formed, and the contact angle meter was used (Coordination Interface Science: The CA-X type) measures the angle (contact angle) between the water droplet and the surface of the wafer, and sets 70 or more to pass. [Experimental Example 1] (1) Preparation of composition As shown in Table 1, as a raw material of the composition, trimethyldecyl dimethylamine as a decylating agent [(CH)3 )3 Si-N (CH3 )2 ] (boiling point: about 86 ° C, the following is called "TMSDMA") 5.0 g, non-butyl butyl ether as a solvent [C4 F9 -O-C2 H5 The mixture (boiling point about 76 ° C, Novec 7200 manufactured by 3M) was mixed at 95.0 g to obtain a composition in a solution state. Namely, a composition ratio of the composition ratio shown in Table 2 was obtained. After the composition was allowed to stand at 25 ° C for 6 hours and allowed to stand for 4 days, no precipitation of insoluble matter or precipitation was observed, showing good stability. (2) Washing the wafer with a smooth thermal oxide film on the wafer (Si wafer with a thermal oxide film layer having a thickness of 1 μm on the surface) in a 1% by mass aqueous solution of hydrofluoric acid at room temperature After immersing for 10 minutes, it was immersed in pure water at room temperature for 1 minute, and immersed in 2-propanol (iPA) at room temperature for 1 minute. (3) Surface treatment of the surface of the wafer by vapor is carried out after the above-mentioned cleaning, and the wafer is placed in the vapor processing chamber in the state of overflowing iPA, and the composition of the prepared solution state is used. The method described below vaporizes and supplies the vapor to the vapor processing chamber. Then, the vapor state is changed to the liquid state of the composition on the surface of the wafer at 60 ° C or lower, and the iPA originally held on the surface of the wafer is replaced with the liquid of the composition. Thereafter, the ruthenium wafer was taken out from the vapor treatment chamber, immersed in iPA at room temperature for 1 minute, and immersed in pure water at room temperature for 1 minute. Finally, the germanium wafer is taken out of the pure water, and air is blown to remove the pure water on the surface. The supply of the vapor of the above composition is carried out in the following manner. In a vaporization chamber heated to 90 ° C (the boiling point of TMSDMA 86 ° C + 4 ° C, without the thermal decomposition of TMSDMA), one side is 2 dm3 The composition of the above-prepared solution state was dropwise added at a flow rate of 0.01 g/sec. The vapor of the composition obtained by vaporization was supplied to the vapor treatment chamber in a nitrogen stream. This treatment was carried out for 60 seconds. The contact angle was evaluated by the point described in the above (B). As a result, as shown in Table 3, the contact angle after the surface treatment of the initial contact angle before the surface treatment was less than 10° was 84°, which showed the water-repellent imparting effect. . [Table 1] [Table 2] [table 3] [Experimental Examples 2 to 7 and Comparative Experimental Examples 1 to 22] As the raw material of the composition, the type of the alkylating agent used in Experimental Example 1, the content of the fluorine-containing ether in the solvent, the type or content of the other solvent, and the acid were changed. The surface treatment of the wafer was carried out in the same manner as in Experimental Example 1 except for the conditions of the type, the concentration, and the temperature of the vaporization chamber. The raw materials, compositions, and evaluation results are shown in Tables 1 to 6. Further, in the table, "TMSDEA" means trimethyldecyldiethylamine, "TFAA" means trifluoroacetic anhydride, and "HMDS" means 1,1,1,3,3,3-hexa. Methyl diazoxide, "TMSTFA" refers to trimethyl decyl trifluoroacetate, "TFA" refers to trifluoroacetic acid, and "TMDS" refers to 1,1,3,3-tetramethyldioxane. "PGMEA" means propylene glycol monomethyl ether acetate, and "DCTFP" means 1,2-dichloro-3,3,3-trifluoropropene. Further, in Experimental Example 2, after the raw materials of the composition were mixed, TMSDMA was reacted with TFAA, and the TFAA as an acid compound of the raw material was consumed by the reaction, thereby obtaining N, N-di which is a by-product of TMSTFA as an acid. The composition shown in Table 2 of methyl-2,2,2-trifluoroacetamide (hereinafter, DMTFAA) and excess TMSDMA. Further, in Comparative Experimental Example 11, after the raw materials of the composition were mixed, HMDS was reacted with TFA, and the TFA of the acid compound as a raw material was consumed by the reaction, thereby obtaining NH as a by-product of TMSTFA as an acid.3 And the composition shown in Table 2 of the excess HMDS. Further, in Comparative Experimental Example 12, after the raw materials of the composition were mixed, HMDS was reacted with TFAA, and the TFAA as an acid compound of the raw material was consumed by the reaction, thereby obtaining a trimethylsulfanyl group as a by-product of TMSTFA as an acid. The composition shown in Table 2 of trifluoroacetamide (hereinafter, TMSTFAA) and excess HMDS. Further, in Comparative Experimental Example 15, after the raw materials of the composition were mixed, TMDS was reacted with TFA, and TFA of the acid compound as a raw material was consumed by the reaction, thereby obtaining NH as a by-product of DMSTFA as an acid.3 And the composition shown in Table 2 of the excess TMDS. Further, in Comparative Experimental Example 16, after the raw materials of the composition were mixed, TMDS was reacted with TFAA, and the TFAA as the acid compound of the raw material was consumed by the reaction, thereby obtaining a dimethyl decyl group as a by-product of DMSTFA as an acid. The composition shown in Table 2 of trifluoroacetamide (hereinafter, DMSTFAA) and the excess TMDS. Further, in Comparative Experimental Example 18, after the raw materials of the composition were mixed, HMDS was reacted with TFA, and the TFA of the acid compound as a raw material was consumed by the reaction, thereby obtaining NH as a by-product of TMSTFA as an acid.3 And the composition shown in Table 5 of the excess HMDS. Further, in Comparative Experimental Example 19, after the raw materials of the composition were mixed, HMDS was reacted with TFAA, and the TFAA as an acid compound of the raw material was consumed by the reaction, thereby obtaining TMSTFA as an acid, TMSTFAA as a by-product, and the like. The composition shown in Table 5 of HMDS. Further, in Comparative Experimental Example 22, after the raw materials of the composition were mixed, TMDS was reacted with TFA, and the TFA of the acid compound as a raw material was consumed by the reaction, thereby obtaining NH as a by-product of DMSTFA as an acid.3 And the composition shown in Table 5 of the excess TMDS. [Table 4] [table 5] [Table 6] The composition specified in the present invention is a solvent having a boiling point lower than the boiling point of the above-described decylating agent, and the fluorinated ether represented by the above formula [2] is from 99.8 to 100% by mass based on 100% by mass of the total amount. Therefore, it can be vaporized at a temperature at which no thermal decomposition of the alkylating agent is caused, and after the raw materials are mixed and allowed to stand at 25 ° C for 6 hours, no precipitation of insoluble matter or formation of precipitates is observed, which is excellent. stability. In the experimental examples 1 and 7 in which the composition was composed of a decylating agent and a fluorine-containing ether, and the experimental example 2 in which the composition was composed of a decylating agent, a fluorine-containing ether, and an acid, the raw materials were mixed at 25 ° C. After standing for 4 days, no precipitation of precipitates or precipitation was observed, and particularly excellent stability was exhibited. Further, Experimental Examples 1 to 7 using the composition specified in the present invention all exhibited a good water repellency imparting effect. On the other hand, in Comparative Experimental Examples 1 to 16 using the composition deviating from the specification of the present invention, the stability of the composition was insufficient (in this case, the contact angle was not evaluated), or the water-repellent imparting effect was not full. In Comparative Examples 17 to 22, an experimental example corresponding to Examples 1 to 6 of Patent Document 1 (Japanese Patent No. 5,486,053) was used, except that the concentration of the alkylating agent was changed to about 5.0% by mass in comparison with the above-mentioned experimental example. Although the water-repellent imparting effect equivalent to the experimental example of the present invention was exhibited, the stability of the composition was insufficient. In addition, since the solvent having a boiling point higher than the boiling point of the protective film forming component is contained in an amount of 3% by mass, the temperature at the time of vaporization is set to be higher than the boiling point of the alkylating agent by 20 ° C or higher, and thus the heat of the alkylating agent is caused. Decomposition.

1‧‧‧晶圓1‧‧‧ wafer

2‧‧‧晶圓表面之微細之凹凸圖案2‧‧‧Microscopic concave and convex pattern on the surface of the wafer

3‧‧‧圖案之凸部3‧‧‧The convex part of the pattern

4‧‧‧圖案之凹部4‧‧‧The recess of the pattern

5‧‧‧凹部之寬度5‧‧‧Width of the recess

6‧‧‧凸部之高度6‧‧‧ Height of the convex part

7‧‧‧凸部之寬度7‧‧‧Width of the convex part

8‧‧‧凹部所保持之液體8‧‧‧Liquid held by the recess

9‧‧‧組合物之蒸氣9‧‧‧Vapor of the composition

10‧‧‧凹部所保持之液體10‧‧‧Liquid held by the recess

11‧‧‧保護膜11‧‧‧Protective film

圖1係對表面製成具有微細凹凸圖案2之面之晶圓1進行斜視時之模式圖。 圖2係表示圖1中之a-a'剖面之一部分者。 圖3係將組合物之蒸氣供至保持有液體之凹部之狀態之模式圖。 圖4係於形成有保護膜之凹部4保持有液體之狀態之模式圖。Fig. 1 is a schematic view showing a state in which a wafer 1 having a surface on which a fine uneven pattern 2 is formed is squinted. Figure 2 is a view showing a portion of the a-a' section of Figure 1. Fig. 3 is a schematic view showing a state in which the vapor of the composition is supplied to a recess in which a liquid is held. Fig. 4 is a schematic view showing a state in which the concave portion 4 in which the protective film is formed holds a liquid.

Claims (24)

一種晶圓之表面處理方法， 其包含於在表面具有凹凸圖案且至少於該凹部具有Si元素之晶圓之洗淨中，於在上述凹凸圖案之至少凹部保持有液體之狀態下，將組合物之蒸氣供至上述於凹凸圖案表面，於晶圓表面使該蒸氣狀態變化為上述組合物之液體狀態，將上述凹部所保持之液體置換為該組合物之液體並保持，藉此至少於上述凹部表面形成撥水性保護膜之步驟，且 上述組合物包含： 下述通式[1]所表示之矽烷化劑；及 沸點低於上述矽烷化劑之沸點之下述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑， 上述矽烷化劑之量相對於該矽烷化劑與溶劑之總量為2～30質量%，[式[1]中，R1 分別相互獨立地為選自碳數為1～10之烴基、及氫元素之一部分或全部被取代為氟元素之碳數為1～8之烴基中之基，R2 分別相互獨立地為選自氫元素之一部分或全部可取代為氟元素之甲基、乙基、乙醯基中之基；x為1～3之整數，y為1～3之整數，4－x－y為0～2之整數]，[式[2]中，Cn F2n ＋ 1 表示碳數n＝4～5之直鏈狀之全氟烷基，Cm H2m ＋ 1 表示碳數m＝2～6之直鏈狀或分枝狀之烷基]。A surface treatment method for a wafer, comprising: a composition having a concave-convex pattern on a surface thereof and at least a wafer having a Si element in the concave portion, wherein the composition is held in a state where at least a concave portion of the concave-convex pattern retains a liquid The vapor is supplied to the surface of the concave-convex pattern, and the vapor state is changed to a liquid state of the composition on the surface of the wafer, and the liquid held by the concave portion is replaced with a liquid of the composition and held thereby at least the concave portion. a step of forming a water-repellent protective film on the surface, and the composition comprises: a decylating agent represented by the following formula [1]; and a formula represented by the following formula [2] having a boiling point lower than a boiling point of the above-described decylating agent; The solvent of the fluorine-containing ether is 99.8 to 100% by mass based on 100% by mass of the total amount, and the amount of the above-mentioned decylating agent is 2 to 30% by mass based on the total amount of the alkylating agent and the solvent. [In the formula [1], R 1 is each independently a hydrocarbon group selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydrocarbon group having a carbon number of 1 to 8 partially or wholly substituted with a fluorine element. R 2 are each independently selected from hydrogen element as a part of or all of the fluorine-substituted methyl, ethyl, acetyl group in the group; x is an integer of 1 to 3, y is an integer of 1 to 3, 4-x-y is an integer from 0 to 2], [In the formula [2], C n F 2n + 1 represents a linear perfluoroalkyl group having a carbon number n = 4 to 5, and C m H 2m + 1 represents a linear number of carbon number m = 2 to 6 or Branched alkyl]. 如請求項1之晶圓之表面處理方法，其中 上述矽烷化劑係選自由(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、C11 H23 Si(CH3 )2 N(CH3 )2 、C12 H25 Si(CH3 )2 N(CH3 )2 、C13 H27 Si(CH3 )2 N(CH3 )2 、C14 H29 Si(CH3 )2 N(CH3 )2 、C15 H31 Si(CH3 )2 N(CH3 )2 、C16 H33 Si(CH3 )2 N(CH3 )2 、C17 H35 Si(CH3 )2 N(CH3 )2 、C18 H37 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(N(CH3 )2 )3 、C2 F5 CH2 CH2 Si(N(CH3 )2 )3 、C3 F7 CH2 CH2 Si(N(CH3 )2 )3 、C4 F9 CH2 CH2 Si(N(CH3 )2 )3 、C5 F11 CH2 CH2 Si(N(CH3 )2 )3 、C6 F13 CH2 CH2 Si(N(CH3 )2 )3 、C7 F15 CH2 CH2 Si(N(CH3 )2 )3 、C8 F17 CH2 CH2 Si(N(CH3 )2 )3 、CF3 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C2 F5 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C3 F7 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C4 F9 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C5 F11 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C6 F13 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C7 F15 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C8 F17 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或上述二甲基胺基矽烷之二甲基胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物所組成之群中之至少1種。A surface treatment method for a wafer according to claim 1, wherein the above-mentioned decylating agent is selected from the group consisting of (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 H 5 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , ( C 3 H 7 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , ( C 4 H 9 ) 3 SiN(CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si(CH 3 ) 2 N(CH 3 ) 2 , C 11 H 23 Si(CH 3 ) 2 N(CH 3 ) 2 , C 12 H 25 Si(CH 3 ) 2 N(CH 3 ) 2 , C 13 H 27 Si(CH 3 ) 2 N(CH 3 ) 2 , C 14 H 29 Si(CH 3 ) 2 N(CH 3 ) 2 , C 15 H 31 Si(CH 3 ) 2 N(CH 3 ) 2 , C 16 H 33 Si(CH 3 ) 2 N(CH 3 ) 2 , C 17 H 35 Si(CH 3 ) 2 N(CH 3 ) 2 , C 18 H 37 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 ) 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N(CH 3 ) 2 , C 2 H 5 Si(H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) (H)N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H)N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 2 F 5 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 3 F 7 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 4 F 9 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 5 F 11 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 6 F 13 CH 2 CH 2 Si(N (CH 3 ) 2 ) 3 , C 7 F 15 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 8 F 17 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , CF 3 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 3 F 7 CH 2 CH 2 Si( CH 3 )(N(CH 3 ) 2 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 )( N(CH 3 ) 2 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 N( CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 , or the dimethylamino group of the above dimethylamino decane (-N(CH 3 ) 2 group) At least one of the group consisting of -N(C 2 H 5 ) 2 , -N(CH 3 )C(O)CH 3 , and -N(CH 3 )C(O)CF 3 . 如請求項1之晶圓之表面處理方法，其中上述通式[1]之-N(R2 )2 所表示之基為-N(CH3 )2 基或-N(C2 H5 )2 基。The surface treatment method of the wafer of claim 1, wherein the group represented by -N(R 2 ) 2 of the above formula [1] is -N(CH 3 ) 2 group or -N(C 2 H 5 ) 2 base. 如請求項1之晶圓之表面處理方法，其中上述矽烷化劑係選自由三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺所組成之群中之至少1種。The surface treatment method for a wafer according to claim 1, wherein the decylating agent is at least one selected from the group consisting of trimethyldecyldimethylamine and trimethyldecyldiethylamine. 如請求項1之晶圓之表面處理方法，其中上述含氟醚為九氟-正丁基乙基醚。The surface treatment method of the wafer of claim 1, wherein the fluorine-containing ether is nonafluoro-n-butyl ethyl ether. 如請求項1之晶圓之表面處理方法，其中上述組合物中之上述矽烷化劑與上述含氟醚之質量比(矽烷化劑/含氟醚)為1/99～30/70。The surface treatment method of the wafer according to claim 1, wherein the mass ratio of the above decylating agent to the above-mentioned fluorine-containing ether in the composition (the alkylating agent/fluorine-containing ether) is from 1/99 to 30/70. 如請求項1之晶圓之表面處理方法，其中上述組合物由上述矽烷化劑及上述含氟醚構成。A surface treatment method for a wafer according to claim 1, wherein the composition is composed of the above-described decylating agent and the above-mentioned fluorine-containing ether. 如請求項1之晶圓之表面處理方法，其中上述組合物進而包含酸。A method of surface treatment of a wafer according to claim 1, wherein the composition further comprises an acid. 如請求項1之晶圓之表面處理方法，其中上述組合物僅由上述矽烷化劑、上述含氟醚及酸構成。A surface treatment method for a wafer according to claim 1, wherein the composition is composed only of the above-described decylating agent, the above-mentioned fluorine-containing ether, and an acid. 如請求項8或9之晶圓之表面處理方法，其中上述酸係選自由三氟乙酸三甲基矽烷酯、三氟甲磺酸三甲基矽烷酯、三氟乙酸二甲基矽烷酯、三氟甲磺酸二甲基矽烷酯、三氟乙酸丁基二甲基矽烷酯、三氟甲磺酸丁基二甲基矽烷酯、三氟乙酸己基二甲基矽烷酯、三氟甲磺酸己基二甲基矽烷酯、三氟乙酸辛基二甲基矽烷酯、三氟甲磺酸辛基二甲基矽烷酯、三氟乙酸癸基二甲基矽烷酯、及三氟甲磺酸癸基二甲基矽烷酯所組成之群中之至少1種。A surface treatment method for a wafer according to claim 8 or 9, wherein the acid is selected from the group consisting of trimethyl decyl trifluoroacetate, trimethyl decyl trifluoromethanesulfonate, dimethyl decyl trifluoroacetate, and the like Dimethyl decyl fluoromethanesulfonate, butyl dimethyl decyl trifluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, hexyl trifluoromethanesulfonate Dimethyl decyl ester, octyl dimethyl decyl trifluoroacetate, octyl dimethyl decyl trifluoromethanesulfonate, decyl dimethyl decyl trifluoroacetate, and decyl dimethyl trifluoromethanesulfonate At least one of the group consisting of decyl esters. 如請求項1之晶圓之表面處理方法，其中上述凹部所保持之液體為非水溶劑。The surface treatment method of the wafer of claim 1, wherein the liquid held by the concave portion is a non-aqueous solvent. 如請求項1之晶圓之表面處理方法，其中至少於上述凹部表面形成撥水性保護膜後，將該凹部所保持之液體狀態之上述組合物藉由乾燥而去除。The surface treatment method of the wafer according to claim 1, wherein the composition in a liquid state held by the concave portion is removed by drying after the water-repellent protective film is formed on at least the surface of the concave portion. 如請求項1之晶圓之表面處理方法，其中至少於上述凹部表面形成撥水性保護膜後，將該凹部所保持之液體狀態之上述組合物置換為與該組合物不同之洗淨液，並將該洗淨液藉由乾燥而去除。The surface treatment method of the wafer according to claim 1, wherein at least the water-repellent protective film is formed on the surface of the concave portion, and the composition in a liquid state held by the concave portion is replaced with a cleaning liquid different from the composition, and The cleaning solution was removed by drying. 如請求項12或13之晶圓之表面處理方法，其中於上述乾燥後之晶圓表面，實施選自由加熱處理、光照射處理、臭氧暴露處理、電漿照射處理、及電暈放電處理所組成之群中之至少1種處理，而將上述撥水性保護膜去除。The surface treatment method of the wafer of claim 12 or 13, wherein the surface of the dried wafer is selected from the group consisting of heat treatment, light irradiation treatment, ozone exposure treatment, plasma irradiation treatment, and corona discharge treatment. The water-repellent protective film is removed by at least one of the treatments. 一種組合物， 其於在表面具有凹凸圖案且至少於該凹部具有Si元素之晶圓之洗淨中，於在上述凹凸圖案之至少凹部保持有液體之狀態下，以蒸氣之形式供至該凹凸圖案表面，於晶圓表面自蒸氣狀態變化為液體狀態，取代上述凹部所保持之液體並保持於該凹部，且該組合物包含： 下述通式[1]所表示之矽烷化劑；及 沸點低於上述矽烷化劑之沸點之下述通式[2]所表示之含氟醚於總量100質量%之中為99.8～100質量%之溶劑， 上述矽烷化劑之量相對於該矽烷化劑與溶劑之總量為2～30質量%，[式[1]中，R1 分別相互獨立地為選自碳數為1～10之烴基、及氫元素之一部分或全部被取代為氟元素之碳數為1～8之烴基中之基，R2 分別相互獨立地為選自氫元素之一部分或全部可取代為氟元素之甲基、乙基、乙醯基中之基；x為1～3之整數，y為1～3之整數，4－x－y為0～2之整數]，[式[2]中，Cn F2n ＋ 1 表示碳數n＝4～5之直鏈狀之全氟烷基，Cm H2m ＋ 1 表示碳數m＝2～6之直鏈狀或分枝狀之烷基]。A composition which is provided in the form of a vapor in a state in which at least a concave portion of the concave-convex pattern is kept in a state in which the surface has a concave-convex pattern and at least the wafer having the Si element in the concave portion is cleaned. The surface of the pattern changes from a vapor state to a liquid state on the surface of the wafer, and replaces the liquid held by the concave portion and is held in the concave portion, and the composition comprises: a decylating agent represented by the following general formula [1]; The solvent of the fluorine-containing ether represented by the following general formula [2], which is less than the boiling point of the above-mentioned sulfonating agent, is 99.8 to 100% by mass based on 100% by mass of the total amount, and the amount of the above-mentioned decylating agent is relative to the oximation. The total amount of the agent and the solvent is 2 to 30% by mass, [In the formula [1], R 1 is each independently a hydrocarbon group selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydrocarbon group having a carbon number of 1 to 8 partially or wholly substituted with a fluorine element. R 2 are each independently selected from hydrogen element as a part of or all of the fluorine-substituted methyl, ethyl, acetyl group in the group; x is an integer of 1 to 3, y is an integer of 1 to 3, 4-x-y is an integer from 0 to 2], [In the formula [2], C n F 2n + 1 represents a linear perfluoroalkyl group having a carbon number n = 4 to 5, and C m H 2m + 1 represents a linear number of carbon number m = 2 to 6 or Branched alkyl]. 如請求項15之組合物，其中 上述矽烷化劑係選自由(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、C11 H23 Si(CH3 )2 N(CH3 )2 、C12 H25 Si(CH3 )2 N(CH3 )2 、C13 H27 Si(CH3 )2 N(CH3 )2 、C14 H29 Si(CH3 )2 N(CH3 )2 、C15 H31 Si(CH3 )2 N(CH3 )2 、C16 H33 Si(CH3 )2 N(CH3 )2 、C17 H35 Si(CH3 )2 N(CH3 )2 、C18 H37 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(N(CH3 )2 )3 、C2 F5 CH2 CH2 Si(N(CH3 )2 )3 、C3 F7 CH2 CH2 Si(N(CH3 )2 )3 、C4 F9 CH2 CH2 Si(N(CH3 )2 )3 、C5 F11 CH2 CH2 Si(N(CH3 )2 )3 、C6 F13 CH2 CH2 Si(N(CH3 )2 )3 、C7 F15 CH2 CH2 Si(N(CH3 )2 )3 、C8 F17 CH2 CH2 Si(N(CH3 )2 )3 、CF3 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C2 F5 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C3 F7 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C4 F9 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C5 F11 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C6 F13 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C7 F15 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、C8 F17 CH2 CH2 Si(CH3 )(N(CH3 )2 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或上述二甲基胺基矽烷之二甲基胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物所組成之群中之至少1種。The composition of claim 15 wherein the above decylating agent is selected from the group consisting of (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 2 H 5 2 Si(CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 3 H 7 2 Si(CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 4 H 9 3 SiN(CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH) 3 ) 2 N(CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si( CH 3 ) 2 N(CH 3 ) 2 , C 11 H 23 Si(CH 3 ) 2 N(CH 3 ) 2 , C 12 H 25 Si(CH 3 ) 2 N(CH 3 ) 2 , C 13 H 27 Si (CH 3 ) 2 N(CH 3 ) 2 , C 14 H 29 Si(CH 3 ) 2 N(CH 3 ) 2 , C 15 H 31 Si(CH 3 ) 2 N(CH 3 ) 2 , C 16 H 33 Si(CH 3 ) 2 N(CH 3 ) 2 , C 17 H 35 Si(CH 3 ) 2 N(CH 3 ) 2 , C 18 H 37 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N(CH 3 ) 2 , C 2 H 5 Si (H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 )(H)N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H)N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 2 F 5 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 3 F 7 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 4 F 9 CH 2 CH 2 Si( N(CH 3 ) 2 ) 3 , C 5 F 11 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 6 F 13 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 7 F 15 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , C 8 F 17 CH 2 CH 2 Si(N(CH 3 ) 2 ) 3 , CF 3 CH 2 CH 2 Si(CH 3 )(N(CH) 3 ) 2 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 )(N(CH 3 ) 2 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 or the dimethylamino group of the above dimethylamino decane (-N(CH 3 ) 2 group) is -N(C 2 H 5 ) 2, -N (CH 3) C (O) CH 3, the group consisting of -N (CH 3) C (O ) CF 3 the compound of the at least one. 如請求項15之組合物，其中上述通式[1]之-N(R2 )2 所表示之基為-N(CH3 )2 基或-N(C2 H5 )2 基。The composition of claim 15, wherein the group represented by -N(R 2 ) 2 of the above formula [1] is a -N(CH 3 ) 2 group or a -N(C 2 H 5 ) 2 group. 如請求項15之組合物，其中上述矽烷化劑係選自由三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺所組成之群中之至少1種。The composition of claim 15, wherein the decylating agent is at least one selected from the group consisting of trimethyldecyldimethylamine and trimethyldecyldiethylamine. 如請求項15之組合物，其中上述含氟醚為九氟-正丁基乙基醚。The composition of claim 15 wherein the above fluorine-containing ether is nonafluoro-n-butyl ethyl ether. 如請求項15之組合物，其中上述組合物中之上述矽烷化劑與上述含氟醚之質量比(矽烷化劑/含氟醚)為1/99～30/70。The composition of claim 15, wherein the mass ratio of the above decylating agent to the above-mentioned fluorine-containing ether in the above composition (the alkylating agent/fluorine-containing ether) is from 1/99 to 30/70. 如請求項15之組合物，其中上述組合物由上述矽烷化劑及上述含氟醚構成。The composition of claim 15 wherein said composition consists of said decylating agent and said fluoroether. 如請求項15之組合物，其中進而包含酸。The composition of claim 15 which further comprises an acid. 如請求項15之組合物，其僅由上述矽烷化劑、上述含氟醚及酸構成。The composition of claim 15 which consists solely of the above decylating agent, the above-mentioned fluorine-containing ether and an acid. 如請求項22或23之組合物，其中上述酸係選自由三氟乙酸三甲基矽烷酯、三氟甲磺酸三甲基矽烷酯、三氟乙酸二甲基矽烷酯、三氟甲磺酸二甲基矽烷酯、三氟乙酸丁基二甲基矽烷酯、三氟甲磺酸丁基二甲基矽烷酯、三氟乙酸己基二甲基矽烷酯、三氟甲磺酸己基二甲基矽烷酯、三氟乙酸辛基二甲基矽烷酯、三氟甲磺酸辛基二甲基矽烷酯、三氟乙酸癸基二甲基矽烷酯、及三氟甲磺酸癸基二甲基矽烷酯所組成之群中之至少1種。The composition of claim 22 or 23, wherein the acid is selected from the group consisting of trimethyl decyl trifluoroacetate, trimethyl decyl trifluoromethanesulfonate, dimethyl decyl trifluoroacetate, trifluoromethanesulfonic acid Dimethyl decyl ester, butyl dimethyl decyl trifluoroacetate, butyl dimethyl decyl trifluoromethanesulfonate, hexyl dimethyl decyl trifluoroacetate, hexyl dimethyl decane triflate Ester, octyl dimethyl decyl trifluoroacetate, octyl dimethyl decyl trifluoromethanesulfonate, decyl dimethyl decyl trifluoroacetate, and decyl dimethyl decyl triflate At least one of the group consisting of.
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