TWI802624B - Surface treatment method, surface treatment agent and method for area-selective film formation on substrate - Google Patents
Surface treatment method, surface treatment agent and method for area-selective film formation on substrate Download PDFInfo
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Abstract
本發明提供一種可對應於具有複數區域之基板表面的各區域材質而以不同改質程度予以改質(例如疏水性之賦予等)的基板表面之表面處理方法、其所用之表面處理劑及使用ALD法於基板上區域選擇性地製膜之方法。 本發明之表面處理方法,其係對基板表面之表面處理方法,且包含使前述表面暴露於包含矽烷化劑(A)及含氮雜環化合物(B)之表面處理劑, 前述表面包含2個以上區域, 2個以上之前述區域中鄰接之區域材質彼此不同, 藉由前述矽烷化劑與2個以上前述區域之反應,使2個以上之前述區域中鄰接之區域之水接觸角彼此不同。The present invention provides a method for surface treatment of a substrate surface that can be modified in different degrees of modification (such as imparting hydrophobicity, etc.) corresponding to the material of each region of the surface of a substrate having a plurality of regions, the surface treatment agent used therefor and its use. The ALD method is a method of area-selective film formation on a substrate. The surface treatment method of the present invention is a surface treatment method for the surface of a substrate, and includes exposing the aforementioned surface to a surface treating agent comprising a silylating agent (A) and a nitrogen-containing heterocyclic compound (B), wherein the aforementioned surface comprises two In the above regions, the materials of the adjacent regions among the two or more aforementioned regions are different from each other, and the water contact angles of the adjacent regions among the two or more aforementioned regions are different from each other by the reaction of the aforementioned silanizing agent with the two or more aforementioned regions.
Description
本發明有關例如半導體積體電路製造等所用之可區域選擇性改質基板表面之表面處理方法,其所用之表面處理劑及使用原子層成長法於基板上區域選擇地製膜的方法。The present invention relates to a surface treatment method for regioselective modification of the substrate surface used in the manufacture of semiconductor integrated circuits, a surface treatment agent used therein, and a method for regioselective film formation on a substrate by atomic layer growth.
近幾年來,半導體裝置之高積體化、微小化的傾向變高,已進展藉由成為遮罩之有機圖型及蝕刻處理而製作之無機圖型之微細化,並要求原子層等級之膜厚控制。 作為於基板上以原子層等級形成薄膜之方法已知有原子層成長法(ALD(Atomic Layer Deposition)法;以下亦簡稱為「ALD法」)。ALD法與一般的CVD(Chemical Vapor Deposition)法比較,已知一併具有高的階差被覆性(step coverage)與膜厚控制性。In recent years, the trend of high integration and miniaturization of semiconductor devices has become higher, and the miniaturization of inorganic patterns produced by organic patterns and etching processes that have become masks has progressed, and films at the atomic layer level are required thick control. Atomic Layer Growth (ALD (Atomic Layer Deposition) method; hereinafter also abbreviated as "ALD method") is known as a method for forming a thin film at the atomic layer level on a substrate. Compared with general CVD (Chemical Vapor Deposition) method, ALD method is known to have high step coverage and film thickness control.
ALD法係於基板上交替供給將構成欲形成的膜之元素作為主成分之2種氣體,於基板上重複數次以原子層單位形成薄膜,而形成期望厚度之膜的薄膜形成技術。 ALD法係於供給原料氣體之時僅1層或數層的原料氣體成分吸附於基板表面,多餘原料氣體無助於成長,而利用成長的自我控制功能(自我限制(self-limiting)功能)。 例如,於基板上形成Al2 O3 膜時,使用由TMA(三甲基鋁)所成之原料氣體與含有O的氧化氣體。又,於基板上形成氮化膜時,替代氧化氣體而使用氮化氣體。 [先前技術文獻] [專利文獻]The ALD method is a thin-film formation technique that alternately supplies two kinds of gases mainly composed of elements constituting the film to be formed on the substrate, and repeats the formation of a thin film on the substrate several times in units of atomic layers to form a film with a desired thickness. In the ALD method, only one or several layers of raw material gas components are adsorbed on the surface of the substrate when the raw material gas is supplied, and the excess raw material gas does not contribute to growth, and the self-control function (self-limiting function) of growth is used. For example, when forming an Al 2 O 3 film on a substrate, a raw material gas composed of TMA (trimethylaluminum) and an oxidizing gas containing O are used. Also, when forming a nitride film on a substrate, a nitride gas is used instead of an oxidizing gas. [Prior Art Document] [Patent Document]
[專利文獻1] 日本專利第4043785號公報 [非專利文獻][Patent Document 1] Japanese Patent No. 4043785 [Non-Patent Document]
[非專利文獻1] J.Phys.Chem.C 2014,118,10957-10962[Non-Patent Document 1] J.Phys.Chem.C 2014,118,10957-10962
[發明欲解決之課題][Problem to be solved by the invention]
近幾年來,已嘗試利用ALD法對基板表面進行區域選擇性地製膜之方法(參考專例文獻1及非專利文獻1)。 伴隨此,要求可較好地適用於藉由ALD法於基板上區域選擇性地製膜方法般之使基板表面區域選擇性地改質之基板。 製膜方法中,藉由利用ALD法,而期待圖型化之原子層等級的膜厚控制、階差被覆性及微細化。In recent years, attempts have been made to form a region-selective film on the substrate surface using the ALD method (see Patent Document 1 and Non-Patent Document 1). Accompanied by this, there is a demand for a substrate that can be better applied to the region-selective modification of the substrate surface region, such as the method of region-selective film formation on the substrate by the ALD method. In the film forming method, by using the ALD method, it is expected to control the film thickness at the atomic layer level, step coverage and miniaturization of patterning.
本發明係鑒於以上狀況而完成者,目的在於提供可對應於具有複數區域之基板表面的各區域材質而以不同改質程度予以改質(例如疏水性之賦予等)的基板表面之表面處理方法、其所用之表面處理劑及使用ALD法於基板上區域選擇性地製膜之方法。 [用以解決課題之手段]The present invention was made in view of the above situation, and the object is to provide a surface treatment method of a substrate surface that can be modified in different degrees of modification (such as imparting hydrophobicity, etc.) corresponding to the material of each region of the substrate surface having a plurality of regions. , the surface treatment agent used therein and the method for forming a region-selective film on the substrate by the ALD method. [Means to solve the problem]
本發明人等發現藉由使用矽烷化劑及含氮雜環化合物進行處理可對應於基板表面材質使改質程度變化,因而完成本發明。亦即,本發明係如以下。The inventors of the present invention found that the degree of modification can be changed according to the surface material of the substrate by treating with a silanizing agent and a nitrogen-containing heterocyclic compound, and thus completed the present invention. That is, the present invention is as follows.
本發明之第1態樣係一種表面處理方法,其係對基板表面之表面處理方法,且包含 使上述表面暴露於包含矽烷化劑(A)及含氮雜環化合物(B)之表面處理劑, 上述表面包含2個以上區域, 2個以上之上述區域中鄰接之區域材質彼此不同, 藉由上述矽烷化劑與2個以上之上述區域之反應,使2個以上之上述區域中鄰接之區域之水接觸角彼此不同。The first aspect of the present invention is a surface treatment method, which is a surface treatment method for the surface of a substrate, and includes exposing the surface to a surface treatment agent containing a silylating agent (A) and a nitrogen-containing heterocyclic compound (B). , The above-mentioned surface includes two or more regions, the adjacent regions in the two or more above-mentioned regions have different materials from each other, and the adjacent regions among the two or more above-mentioned regions are made The water contact angles are different from each other.
本發明之第2態樣係一種表面處理劑,其係如第1態樣之表面處理方法中所使用之表面處理劑,且包含矽烷化劑(A)及含氮雜環化合物(B)。The second aspect of the present invention is a surface treatment agent, which is the surface treatment agent used in the surface treatment method of the first aspect, and contains a silylation agent (A) and a nitrogen-containing heterocyclic compound (B).
本發明之第3態樣係一種基板表面之區域選擇性製膜方法,其包含藉由第1態樣之表面處理方法,處理上述基板之上述表面;及 於經表面處理之上述基板之表面藉由原子層成長法形成膜, 使上述膜之材料堆積量區域選擇性地不同。 [發明效果]The third aspect of the present invention is a region-selective film-forming method on the surface of a substrate, which includes treating the above-mentioned surface of the above-mentioned substrate by the surface treatment method of the first aspect; The film is formed by the atomic layer growth method, and the material deposition amount of the above film is selectively different from region to region. [Invention effect]
本發明之表面處理方法可提供可對應於具有複數區域之基板表面的各區域材質而以不同改質程度予以改質(例如疏水性之賦予等),尤其可較好地適用於使用ALD法之基板表面之區域選擇性地製膜的基板。 本發明之表面處理劑可提供上述表面處理方法。 本發明之於基板上區域選擇性地製膜方法能以原子層等級之膜厚控制而於基板上區域選擇性地製膜階差被覆性優異之膜。The surface treatment method of the present invention can provide different modification degrees corresponding to the material of each region of the substrate surface with multiple regions (such as imparting hydrophobicity, etc.), and is especially suitable for the use of ALD method. A substrate on which a film is selectively formed on a region of the substrate surface. The surface treatment agent of the present invention can provide the above-mentioned surface treatment method. The region-selective film formation method on the substrate of the present invention can selectively form a film with excellent step coverage on the substrate by controlling the film thickness at the atomic layer level.
以下,針對本發明之實施態樣詳細說明,但本發明絕非限定於以下實施態樣,在本發明目的之範圍內,可加以適當變更而實施。Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is by no means limited to the following embodiments, and can be implemented with appropriate changes within the scope of the purpose of the present invention.
<<對基板表面之表面處理方法>> 第1態樣之表面處理方法係對基板表面之表面處理方法,且包含 使上述表面暴露於包含矽烷化劑(A)及含氮雜環化合物(B)之表面處理劑, 上述表面包含2個以上區域, 2個以上之上述區域中鄰接之區域材質彼此不同, 藉由上述矽烷化劑與2個以上之上述區域之反應,使2個以上之上述區域中鄰接之區域之水接觸角彼此不同。<<Surface treatment method for the surface of the substrate>> The surface treatment method of the first aspect is a surface treatment method for the surface of the substrate, and includes exposing the above-mentioned surface to a silylating agent (A) and a nitrogen-containing heterocyclic compound (B). ) surface treatment agent, the above-mentioned surface includes two or more regions, the materials of adjacent regions in the two or more above-mentioned regions are different from each other, and the two or more above-mentioned regions are made The water contact angles of adjacent regions among the regions are different from each other.
作為成為表面處理對象之「基板」,例示有用於製作半導體裝置所使用之基板,例如矽(Si)基板、氮化矽(SiN)基板、矽氧化膜(Ox)基板、鎢(W)基板、鈷(Co)基板、氮化鈦(TiN)基板、氮化鉭(TaN)基板、鍺(Ge)基板、矽鍺(SiGe)基板、鋁(Al)基板、鎳(Ni)基板、釕(Ru)基板、銅(Cu)基板等。 所謂「基板表面」除了基板本身之表面以外,亦可舉例為基板上所設之無機圖型及有機圖型之表面以及未經圖型化之無機層或有機層之表面。Examples of the "substrate" to be subjected to surface treatment include substrates used for manufacturing semiconductor devices, such as silicon (Si) substrates, silicon nitride (SiN) substrates, silicon oxide film (Ox) substrates, tungsten (W) substrates, Cobalt (Co) substrate, titanium nitride (TiN) substrate, tantalum nitride (TaN) substrate, germanium (Ge) substrate, silicon germanium (SiGe) substrate, aluminum (Al) substrate, nickel (Ni) substrate, ruthenium (Ru ) substrate, copper (Cu) substrate, etc. In addition to the surface of the substrate itself, the so-called "substrate surface" can also be, for example, the surface of the inorganic pattern and the organic pattern provided on the substrate, and the surface of the non-patterned inorganic layer or organic layer.
作為基板上所設之無機圖型例示有使用光阻法於基板中存在之無機層表面製作蝕刻遮罩,隨後,藉由蝕刻處理形成之圖型。作為無機層除了基板本身表面以外,亦可例示構成基板之元素的氧化膜、於基板表面形成之SiN、Ox、W、Co、TiN、TaN、Ge、SiGe、Al、Ni、Ru、Cu等之無機物的膜或層等。 作為此等膜或層並未特別限定,但可例示於半導體裝置之製作過程中以形成之無機物的膜或層等。An example of the inorganic pattern provided on the substrate is a pattern formed by forming an etching mask on the surface of the inorganic layer existing in the substrate using a photoresist method, and then etching. In addition to the surface of the substrate itself, examples of the inorganic layer include oxide films of elements constituting the substrate, SiN, Ox, W, Co, TiN, TaN, Ge, SiGe, Al, Ni, Ru, Cu, etc. formed on the surface of the substrate. A film or layer of an inorganic substance, etc. These films or layers are not particularly limited, but examples include films or layers of inorganic substances formed in the process of manufacturing semiconductor devices.
作為基板上所設之有機圖型例示有使用光阻等藉由光微影法於基板上形成之樹脂圖型等。此等有機圖型例如可藉由於基板上形成光阻的膜之有機層,對該有機層透過光罩進行曝光並顯像而形成。作為有機層除了基板本身表面以外,亦可為設於基板表面之積層膜的表面等所設之有機層。作為此等有機層並未特別限定,但可例示於半導體裝置之製作過程中,用以形成蝕刻遮罩所設之有機物的膜。Examples of the organic pattern provided on the substrate include a resin pattern formed on the substrate by photolithography using a photoresist or the like. These organic patterns can be formed, for example, by forming an organic layer of a photoresist film on a substrate, exposing and developing the organic layer through a photomask. In addition to the surface of the substrate itself, the organic layer may be an organic layer provided on the surface of a laminated film provided on the surface of the substrate or the like. These organic layers are not particularly limited, but examples include films of organic substances used to form etching masks provided in the manufacturing process of semiconductor devices.
(基板表面包含2個區域的態樣) 第1態樣之表面處理方法係基板表面包含2個以上之區域,上述2個以上之區域中鄰接的區域彼此材質不同。(Aspect in which the surface of the substrate includes two regions) In the surface treatment method of the first aspect, the surface of the substrate includes two or more regions, and the adjacent regions of the two or more regions have different materials from each other.
上述2個以上之區域間,作為水的接觸角(較好為疏水性)較其他區域大的傾向之區域,舉例為包含自Si、SiN、Ox、TiN、TaN、Ge及SiGe所組成之群中選擇之至少1種的區域。 上述2個以上之區域間,作為水的接觸角(較好為疏水性)較其他區域小的傾向之區域,舉例為包含自W、Co、Al、Ni、Ru、Cu、TiN及TaN所組成之群中選擇之至少1種的區域。Between the above two or more regions, the region where the contact angle of water (preferably hydrophobicity) tends to be larger than the other regions is, for example, a group consisting of Si, SiN, Ox, TiN, TaN, Ge, and SiGe An area of at least one of the selected ones. Between the above two or more regions, as a region where the contact angle of water (preferably hydrophobicity) tends to be smaller than that of other regions, for example, it is composed of W, Co, Al, Ni, Ru, Cu, TiN, and TaN. An area of at least one selected from the group.
例如,將上述2個以上之區域中之1個區域設為第1區域,將與其鄰接之區域設為第2區域時,第1區域與第2區域之材質不同。 此處,第1區域與第2區域各亦可分割為複數區域,亦可不分割。 作為第1區域與第2區域之例,舉例為例如將基板本身表面設為第1區域,將基板表面形成之無機層表面設為第2區域之態樣,將基板表面形成之第1無機層表面設為第1區域,將形成於基板表面之第2無機層表面設為第2區域之態樣等。又,同樣亦可舉例為替代該等無機層之形成,而形成有機層之態樣等。 作為將基板本身表面設為第1區域,將基板表面形成之無機層表面設為第2區域之態樣,基於基板表面之材質不同的2個以上之鄰接區域間選擇性提高疏水性且提高水的接觸角之差的觀點,較好為將自Si基板、SiN基板、Ox基板、TiN基板、TaN基板、Ge基板及SiGe基板所組成之群中選擇之至少1種基板表面設為第1區域,將於上述基板表面形成之包含自W、Co、Al、Ni、Ru、Cu、TiN及TaN所組成之群中選擇之至少1種的無機層的表面設為第2區域之態樣。 又,作為將基板表面形成之第1無機層表面設為第1區域,將形成於基板表面之第2無機層表面設為第2區域之態樣,基於基板表面之材質不同的2個以上之鄰接區域間選擇性提高疏水性且提高水的接觸角之差的觀點,較好為將於任意基板(例如Si基板)表面形成之包含自SiN、Ox、TiN、TaN、Ge及SiGe所組成之群中選擇之至少1種的第1無機層的表面設為第1區域,將於上述基板表面形成之包含自W、Co、Al、Ni、Ru、Cu、TiN及TaN所組成之群中選擇之至少1種的第2無機層的表面設為第2區域之態樣。For example, when one of the above two or more regions is set as the first area and the adjacent area is set as the second area, the materials of the first area and the second area are different. Here, each of the first area and the second area may be divided into plural areas, or may not be divided. As an example of the first region and the second region, for example, the surface of the substrate itself is set as the first region, and the surface of the inorganic layer formed on the surface of the substrate is set as the second region, and the first inorganic layer formed on the surface of the substrate is The surface is defined as the first region, and the surface of the second inorganic layer formed on the surface of the substrate is defined as the second region. Also, similarly, an aspect in which an organic layer is formed instead of the formation of these inorganic layers can also be exemplified. As an aspect in which the surface of the substrate itself is used as the first region and the surface of the inorganic layer formed on the surface of the substrate is used as the second region, the water repellency can be selectively improved between two or more adjacent regions with different materials on the substrate surface, and water repellency can be improved. From the viewpoint of the difference in contact angle, it is preferable to set the surface of at least one substrate selected from the group consisting of Si substrate, SiN substrate, Ox substrate, TiN substrate, TaN substrate, Ge substrate, and SiGe substrate as the first region. The surface of the inorganic layer comprising at least one selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN formed on the surface of the substrate is set as the second region. In addition, as an aspect in which the surface of the first inorganic layer formed on the surface of the substrate is set as the first region, and the surface of the second inorganic layer formed on the surface of the substrate is set as the second region, based on two or more substrates having different materials on the surface of the substrate, From the viewpoint of selectively increasing hydrophobicity between adjacent regions and increasing the difference in contact angle of water, it is preferable to form a substrate composed of SiN, Ox, TiN, TaN, Ge, and SiGe to be formed on the surface of any substrate (such as a Si substrate). The surface of the first inorganic layer of at least one selected from the group is set as the first region, and is selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN to be formed on the surface of the above-mentioned substrate. The surface of the at least one second inorganic layer is in the form of the second region.
(基板表面包含3個區域的態樣) 將上述2個以上之區域中之1個區域設為第1區域,與其鄰接之區域設為第2區域,進而將與第2區域鄰接之區域設為第3區域時,第1區域與第2區域彼此材質不同,第2區域與第3區域彼此材質不同。 此處,第1區域與第3區域鄰接時,第1區域與第3區域彼此材質不同。 第1區域與第3區域未鄰接時,第1區域與第3區域彼此材質可不同亦可相同。 又,第1區域、第2區域及第3區域各亦可分割為複數區域,亦可不分割。 作為第1區域、第2區域及第3區域之例,舉例為例如將基板本身表面設為第1區域,將基板表面形成之第1無機層表面設為第2區域,將基板表面形成之第2無機層表面設為第3區域之態樣等。又,同樣亦可舉例為替代該等無機層之形成,而形成有機層之態樣等。又亦同樣可舉例為僅將第2無機層及第3無機層之任一者變為有機層而形成般之包含無機層及有機層兩者之態樣等。 基於基板表面之材質不同的2個以上之鄰接區域間選擇性提高疏水性且提高水的接觸角之差的觀點,較好為將任意基板(例如Si基板)本身表面設為第1區域,於上述基板表面所形成之包含自SiN、Ox、TiN、TaN、Ge及SiGe所組成之群中選擇之至少1種的第1無機層的表面設為第2區域,將於上述基板表面形成之包含自W、Co、Al、Ni、Ru、Cu、TiN及TaN所組成之群中選擇之至少1種的第2無機層的表面設為第3區域之態樣。 關於存在第4個以上區域之情況,亦可適用同樣思考方法。 材質不同之區域數的上限值,只要不損及本發明效果則無任何限制,例如可為7以下或6以下,典型上為5以下。(Aspects where the surface of the substrate includes three regions) One of the above two or more regions is defined as the first region, the region adjacent to it is defined as the second region, and the region adjacent to the second region is defined as In the case of the third area, the materials of the first area and the second area are different from each other, and the materials of the second area and the third area are different from each other. Here, when the first area and the third area are adjacent, the materials of the first area and the third area are different from each other. When the first area and the third area are not adjacent, the materials of the first area and the third area can be different or the same. Also, each of the first area, the second area, and the third area may be divided into plural areas, or may not be divided. As examples of the first area, the second area, and the third area, for example, the surface of the substrate itself is set as the first area, the surface of the first inorganic layer formed on the surface of the substrate is set as the second area, and the surface of the first inorganic layer formed on the surface of the substrate is set as the second area. 2. The surface of the inorganic layer is set in the form of the third region, etc. Also, similarly, an aspect in which an organic layer is formed instead of the formation of these inorganic layers can also be exemplified. In addition, an embodiment including both the inorganic layer and the organic layer can be similarly exemplified by changing only any one of the second inorganic layer and the third inorganic layer into an organic layer. From the viewpoint of selectively increasing hydrophobicity and increasing the difference in contact angle of water between two or more adjacent regions with different materials on the surface of the substrate, it is preferable to set the surface of any substrate (such as a Si substrate) itself as the first region, and The surface of the first inorganic layer comprising at least one selected from the group consisting of SiN, Ox, TiN, TaN, Ge, and SiGe formed on the surface of the above-mentioned substrate is set as the second region, and the surface of the above-mentioned substrate including The surface of the second inorganic layer of at least one selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN is set as the third region. The same way of thinking can also be applied to the case where there are four or more regions. The upper limit of the number of regions with different materials is not limited as long as it does not impair the effect of the present invention. For example, it can be 7 or less or 6 or less, typically 5 or less.
(暴露) 作為使基板表面暴露於表面處理劑之方法,舉例為將可包含溶劑之表面處理劑(典型上為液狀的表面處理劑)藉由例如浸漬法或旋轉塗佈法、輥塗佈法及刮板法等之塗佈法等之手段,應用(例如塗佈)於基板表面而暴露之方法。 作為暴露溫度例如為10℃以上90℃以下,較好為20℃以上80℃以下,更好為30℃以上70℃以下,又更好為40℃以上60℃以下。 作為上述暴露時間,基於基板表面之材質不同的2個以上之鄰接區域間選擇性提高疏水性之觀點,較好為20秒以上,更好為1分鐘以上,又,更好為10分鐘以上。 上述暴露時間之上限值並未特別限制,但可為例如6小時以下等,典型上為2小時以下。 上述暴露後可根據需要進行洗淨(例如以水、活性劑清洗等之洗淨)及/或乾燥(以氮吹拂等之洗淨)。 例如,作為具備無機圖型或有機圖型之基板表面之以洗淨液之洗淨處理,可直接採用以往無機圖型或有機圖型之洗淨處理所使用之洗淨液本身,關於無機圖型舉例為SPM(硫酸・過氧化氫水溶液)、APM(氨・過氧化氫水溶液)等,關於有機圖型舉例為水、活性劑清洗液等。 且,對於乾燥後之處理基板亦可根據需要追加100℃以上300℃以下之加熱處理。(Exposure) As a method of exposing the substrate surface to a surface treatment agent, for example, a surface treatment agent (typically a liquid surface treatment agent) that may contain a solvent is applied by, for example, a dipping method, a spin coating method, or a roll coating method. A method of applying (for example, coating) on the surface of a substrate and exposing it by means of coating methods such as the blade method and the doctor blade method. The exposure temperature is, for example, from 10°C to 90°C, preferably from 20°C to 80°C, more preferably from 30°C to 70°C, more preferably from 40°C to 60°C. The above-mentioned exposure time is preferably at least 20 seconds, more preferably at least 1 minute, and more preferably at least 10 minutes, from the viewpoint of selectively improving hydrophobicity between two or more adjacent regions of different materials on the surface of the substrate. The upper limit of the exposure time is not particularly limited, but may be, for example, 6 hours or less, typically 2 hours or less. After the above-mentioned exposure, cleaning (such as cleaning with water, active agent cleaning, etc.) and/or drying (cleaning with nitrogen blowing, etc.) can be carried out as necessary. For example, as the cleaning treatment of the surface of the substrate with inorganic patterns or organic patterns, the cleaning solution itself used in the cleaning treatment of inorganic patterns or organic patterns can be directly used. Regarding inorganic patterns Examples of molds include SPM (sulfuric acid-hydrogen peroxide solution), APM (ammonia-hydrogen peroxide solution), etc., and examples of organic patterns include water, active agent cleaning solution, etc. Also, heat treatment at 100°C to 300°C can be added to the processed substrate after drying as needed.
藉由上述暴露,可對應於基板表面之各區域的材質區域選擇性地矽烷化。 表面處理劑暴露後之基板表面對水之接觸角,可設為5°以上140°以下。 藉由控制基板表面之材質、矽烷化劑(A)及含氮雜環化合物(B)之種類及使用量以及暴露條件等,可將對水之接觸角設為50°以上,較好為60°以上,更好為70°以上,又更好為90°以上,特佳為100°以上,最好為101°以上。 作為上述接觸角之上限值並未特別限制,但為例如140°以下,典型上為130°以下。Through the above-mentioned exposure, the material area corresponding to each area on the surface of the substrate can be selectively silanized. After the surface treatment agent is exposed, the contact angle of the substrate surface to water can be set at 5° to 140°. By controlling the material of the substrate surface, the type and amount of silanizing agent (A) and nitrogen-containing heterocyclic compound (B), and exposure conditions, the contact angle to water can be set to 50° or more, preferably 60° ° or more, more preferably 70° or more, more preferably 90° or more, particularly preferably 100° or more, most preferably 101° or more. The upper limit of the contact angle is not particularly limited, but is, for example, 140° or less, typically 130° or less.
第1態樣之表面處理方法,因基板表面之2個以上鄰接之區域間材質不同,藉由上述暴露,可於上述2個以上鄰接之區域間選擇性提高疏水性,可使水的接觸角彼此不同。 作為上述2個以上鄰接之區域間的水的接觸角之差,只要不損及本發明之效果,則未特別限制,舉例為例如10°以上,基於上述2個以上之鄰接區域間選擇性提高疏水性之觀點,上述水的接觸角差較好為20°以上,更好為30°以上,又更好為40°以上。 作為上述接觸角差的上限值,只要不損及本發明之效果,則未特別限制,舉例為例如80°以下或70°以下,典型上為60°以下。In the surface treatment method of the first aspect, since the materials of two or more adjacent regions on the surface of the substrate are different, the above-mentioned exposure can selectively increase the hydrophobicity between the above two or more adjacent regions, and the contact angle of water can be improved. different from each other. The difference in water contact angle between the two or more adjacent regions is not particularly limited as long as it does not impair the effect of the present invention, for example, it is 10° or more, based on the selectivity improvement between the above two or more adjacent regions From the viewpoint of hydrophobicity, the difference in the contact angle of water is preferably at least 20°, more preferably at least 30°, still more preferably at least 40°. As the upper limit of the above-mentioned contact angle difference, as long as it does not impair the effect of the present invention, it is not particularly limited, for example, it is 80° or less or 70° or less, and typically it is 60° or less.
<表面處理劑> 接著,針對第1態樣之表面處理方法所用之表面處理劑加以說明。 本態樣之表面處理劑包含矽烷化劑(A)及含氮雜環化合物(B), 以下針對各成分加以說明。<Surface treatment agent> Next, the surface treatment agent used in the surface treatment method of the first aspect will be described. The surface treatment agent of this aspect includes a silanizing agent (A) and a nitrogen-containing heterocyclic compound (B). The following describes each component.
[矽烷化劑(A)] 矽烷化劑(A)係用以將基板表面矽烷化,增大基板表面之疏水性的成分。 作為矽烷化劑(A)並未特別限定,可使用以往習知之所有矽烷化劑。作為此等矽烷化劑,可使用例如具有鍵結於矽原子的疏水性基的烷氧基單矽烷化合物、具有鍵結於矽原子的疏水性基與鍵結於矽原子之離去基的化合物(更詳言之,例如以後述通式(2)表示之化合物等)。[Silylation agent (A)] The silanization agent (A) is a component used to silanize the substrate surface to increase the hydrophobicity of the substrate surface. The silylating agent (A) is not particularly limited, and all known silanizing agents can be used. As such silylating agents, for example, alkoxymonosilane compounds having a hydrophobic group bonded to a silicon atom, compounds having a hydrophobic group bonded to a silicon atom and a leaving group bonded to a silicon atom can be used (In more detail, for example, a compound represented by the general formula (2) described below, etc.).
(具有鍵結於矽原子的疏水性基的烷氧基單矽烷化合物) 具有鍵結於矽原子的疏水性基的烷氧基單矽烷化合物意指具有1個矽原子,具有鍵結於上述矽原子之至少1個疏水性基,且具有鍵結於上述矽原子之至少1個烷氧基之化合物。 藉由使用具有鍵結於矽原子的疏水性基的烷氧基單矽烷化合物作為矽烷化劑(A),可將具有疏水性基的烷氧基單矽烷化合物結合於基板表面。藉由使烷氧基單矽烷化合物結合於基板表面,可於基板表面形成源自烷氧基單矽烷化合物之單分子膜。該單分子膜較好為於基板之面方向形成矽氧烷鍵結之網絡之自我組織化單分子膜(self-assembled monolayer;SAM)。單分子膜及自我組織化單分子膜將於後詳述。(Alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom) The alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom means having one silicon atom and having A compound having at least one hydrophobic group on an atom and at least one alkoxy group bonded to the aforementioned silicon atom. By using an alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom as the silylating agent (A), the alkoxymonosilane compound having a hydrophobic group can be bonded to the substrate surface. By binding the alkoxymonosilane compound to the substrate surface, a monomolecular film derived from the alkoxymonosilane compound can be formed on the substrate surface. The monomolecular film is preferably a self-assembled monomolecular film (self-assembled monolayer; SAM) in which a network of siloxane bonds is formed in the plane direction of the substrate. The monomolecular film and the self-organized monomolecular film will be described in detail later.
作為上述烷氧基單矽烷化合物所具有之上述疏水性基,基於基板表面之材質不同的2個以上之鄰接區域間選擇性提高疏水性之觀點,較好為碳原子數3以上20以下之鏈狀脂肪族烴基,更好為碳原子數6以上18以下之鏈狀脂肪族烴基,又更好為碳原子數7以上12以下之鏈狀脂肪族烴基,特佳為碳原子數8以上11以下之鏈狀脂肪族烴基,最好為碳原子數8以上10以下之鏈狀脂肪族烴基。 上述鏈狀脂肪族烴基之氫原子的一部分或全部可經鹵原子(氟原子等)取代,可為直鏈狀亦可為分支鏈狀,但較好為氫原子的一部分或全部可經氟原子取代之直鏈狀脂肪族烴基。The above-mentioned hydrophobic group possessed by the above-mentioned alkoxymonosilane compound is preferably a chain having 3 to 20 carbon atoms from the viewpoint of selectively improving hydrophobicity between two or more adjacent regions having different materials on the surface of the substrate. An aliphatic hydrocarbon group, more preferably a chain aliphatic hydrocarbon group with 6 to 18 carbon atoms, more preferably a chain aliphatic hydrocarbon group with 7 to 12 carbon atoms, particularly preferably a chain aliphatic hydrocarbon group with 8 to 11 carbon atoms The chain aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group having 8 to 10 carbon atoms. A part or all of the hydrogen atoms of the above-mentioned chain aliphatic hydrocarbon group may be substituted by halogen atoms (fluorine atoms, etc.), and may be linear or branched, but preferably a part or all of the hydrogen atoms may be substituted by fluorine atoms. Substituted linear aliphatic hydrocarbon group.
上述烷氧基單矽烷化合物所具有之烷氧基係以通式RO-(R表示烷基)表示,作為以該R表示之烷基,較好為直鏈或分支烷基,更好為直鏈烷基。且,以該R表示之烷基之碳原子數並未特別限定,但尤其基於水解、縮合時之控制之觀點,較好為1以上10以下,更好為1以上5以下,又更好為1或2。作為烷氧基單矽烷化合物所具有之烷氧基,具體可舉例為甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基及第三丁氧基等。The alkoxy group of the alkoxymonosilane compound mentioned above is represented by the general formula RO-(R represents an alkyl group). As the alkyl group represented by this R, it is preferably a linear or branched alkyl group, more preferably a straight chain group. Alkanes. In addition, the number of carbon atoms of the alkyl group represented by R is not particularly limited, but it is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from the viewpoint of controlling hydrolysis and condensation. 1 or 2. As the alkoxy group of the alkoxy monosilane compound, specific examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy and third butoxy wait.
作為上述烷氧基單矽烷化合物較好為以下述式(1)表示之化合物。(上述通式中,R1 各獨立為1價有機基,R1 中之至少1個係氫原子之一部分或全部可經氟原子取代之碳原子數3以上20以下之鏈狀脂肪族烴基,X係烷氧基,n為1以上3以下之整數)。 作為R1 之1價有機基舉例為烷基、芳香族烴基、胺基、單烷胺基、二烷胺基等。As the above-mentioned alkoxymonosilane compound, a compound represented by the following formula (1) is preferable. (In the above general formula, each of R1 is independently a monovalent organic group, and at least one of R1 is a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms that can be replaced by a part or all of hydrogen atoms, X is an alkoxy group, and n is an integer ranging from 1 to 3). The monovalent organic group as R 1 is exemplified by an alkyl group, an aromatic hydrocarbon group, an amino group, a monoalkylamino group, a dialkylamino group, and the like.
以下針對R1 係氫原子之一部分或全部可經氟原子取代之碳原子數3以上20以下之鏈狀脂肪族烴基以外之有機基的情況加以說明。 作為上述烷基較好為碳原子數1以上20以下(較好為碳原子數1以上8以下)之直鏈狀或分支鏈狀烷基,更好為甲基、乙基、正丙基及異丙基。 作為上述芳香族烴基較好為苯基、萘基、聯苯基、蒽基及菲基,更好為苯基及萘基,特佳為苯基。 上述單烷胺基或二烷胺基中所含之烷基於鏈中亦可包含氮原子、氧原子或羰基,可為直鏈烷基亦可為分支鏈烷基。單烷胺基或二烷胺基中所含之烷基之碳原子數並未特別限定,較好為1以上20以下,更好為1以上10以下,特佳為1以上6以下。The following describes the case where R1 is an organic group other than a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms, in which part or all of the hydrogen atoms may be substituted by fluorine atoms. The above-mentioned alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms (preferably having 1 to 8 carbon atoms), more preferably methyl, ethyl, n-propyl and Isopropyl. As the above-mentioned aromatic hydrocarbon group, phenyl, naphthyl, biphenyl, anthracenyl and phenanthrenyl are preferred, phenyl and naphthyl are more preferred, and phenyl is particularly preferred. The alkyl group contained in the above-mentioned monoalkylamino group or dialkylamino group may also contain a nitrogen atom, an oxygen atom or a carbonyl group in the chain, and may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamino group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6.
其次,針對R1 係氫原子之一部分或全部可經氟原子取代之碳原子數3以上20以下之鏈狀脂肪族烴基之情況加以說明。 該鏈狀脂肪族烴基之碳原子數,如前述,更好為碳原子數6以上18以下,又更好為7以上12以下,特佳為8以上11以下,最好為8以上10以下。 該鏈狀脂肪族烴基可為直鏈狀,亦可為分支鏈狀,較好為直鏈狀。 作為上述之氫原子之一部分或全部可經氟原子取代之鏈狀脂肪族烴基之較佳例舉例為正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基及正十八烷基等之直鏈烷基,及該等之直鏈烷基上的氫原子經氟原子取代之氟化直鏈烷基。Next, the case where R 1 is a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms in which part or all of the hydrogen atoms may be substituted by fluorine atoms will be described. The number of carbon atoms in the chain aliphatic hydrocarbon group is, as described above, more preferably from 6 to 18, more preferably from 7 to 12, particularly preferably from 8 to 11, most preferably from 8 to 10. The chain aliphatic hydrocarbon group may be linear or branched, preferably linear. Preferable examples of chain aliphatic hydrocarbon groups in which part or all of the above-mentioned hydrogen atoms may be substituted by fluorine atoms are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl , straight-chain alkyl groups such as n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl, and Fluorinated straight-chain alkyl groups in which hydrogen atoms on the straight-chain alkyl groups are replaced by fluorine atoms.
作為X,較好為碳原子數1以上5以下之烷氧基。作為X之具體例舉例為甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基等之烷氧基。 該等中,尤其基於水解、縮合時之控制之觀點,較好為甲氧基、乙氧基、異丙氧基或丁氧基。 又,上述烷氧基單矽烷化合物較好為三烷氧基單矽烷化合物。X is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of X include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, and 3-butoxy. Among these, methoxy, ethoxy, isopropoxy or butoxy are preferred especially from the viewpoint of control during hydrolysis and condensation. Also, the above-mentioned alkoxymonosilane compound is preferably a trialkoxymonosilane compound.
上述例示之烷氧基單矽烷化合物可單獨使用或混合2種以上使用。 作為此等烷氧基單矽烷化合物之具體例舉例為丙基三甲氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、正己基三甲氧基矽烷、正辛基三甲氧基矽烷、正十二烷基三甲氧基矽烷、正十八烷基三甲氧基矽烷等,較好為正己基三甲氧基矽烷、正辛基三甲氧基矽烷、正十二烷基三甲氧基矽烷或正十八烷基三甲氧基矽烷,更好為正辛基三甲氧基矽烷、正十二烷基三甲氧基矽烷或正十八烷基三甲氧基矽烷。The above-exemplified alkoxymonosilane compounds may be used alone or in combination of two or more. Specific examples of such alkoxymonosilane compounds include propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane , n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, etc., preferably n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane or n-octadecyltrimethoxysilane, more preferably n-octyltrimethoxysilane, n-dodecyltrimethoxysilane or n-octadecyltrimethoxysilane.
藉由使用上述之烷氧基單矽烷化合物,可於基板表面形成單分子膜。於基板表面形成源自具有疏水性基之烷氧基單矽烷化合物的單分子膜時,可高度提高基板表面之疏水性,其結果,可提高基板表面之材質不同之2個以上鄰接之區域間疏水性提高之選擇性。 尤其基於高度提高疏水性之觀點,單分子膜中,較好於基板之面方向形成矽氧烷鍵結之網絡。該單分子膜為所謂自我組織化單分子膜。自我組織化單分子膜中,較密地含有源自烷氧基單矽烷化合物之殘基,由於該殘基彼此藉由矽氧烷鍵而鍵結,故單分子膜可強固結合於基板表面。其結果,尤其可展現高度疏水性提高。 該自我組織化單分子膜如前述,可藉由使用三烷氧基單矽烷化合物及/或二烷氧基單矽烷化合物作為矽烷化劑(A)而形成。By using the above-mentioned alkoxymonosilane compound, a monomolecular film can be formed on the surface of the substrate. When a monomolecular film derived from an alkoxy monosilane compound having a hydrophobic group is formed on the substrate surface, the hydrophobicity of the substrate surface can be highly improved, and as a result, the gap between two or more adjacent regions with different materials on the substrate surface can be improved. Selectivity for enhanced hydrophobicity. In particular, from the viewpoint of highly improving hydrophobicity, in the monomolecular film, it is preferable to form a network of siloxane bonds in the plane direction of the substrate. This monomolecular film is a so-called self-organized monomolecular film. In the self-organized monomolecular film, the residues derived from the alkoxymonosilane compound are densely contained, and since the residues are bonded to each other through siloxane bonds, the monomolecular film can be strongly bonded to the surface of the substrate. As a result, especially high hydrophobicity can be exhibited. As mentioned above, the self-organized monomolecular film can be formed by using a trialkoxymonosilane compound and/or a dialkoxymonosilane compound as the silylating agent (A).
形成上述單分子膜可藉由例如膜厚變化、接觸角變化、X射線光電子分光(XPS)而確認。 又,作為上述疏水性之單分子膜的膜厚可設為例如20nm以下,較好為10nm以下,更好為5nm以下,又更好為3nm以下。作為下限值,只要不損及本發明之效果,並未特別限制,但例如為0.1nm以上,典型上為0.5nm以上。Formation of the monomolecular film can be confirmed by, for example, changes in film thickness, changes in contact angle, and X-ray photoelectron spectroscopy (XPS). Also, the film thickness of the above-mentioned hydrophobic monomolecular film can be, for example, 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and more preferably 3 nm or less. The lower limit is not particularly limited unless the effect of the present invention is impaired, but is, for example, 0.1 nm or more, typically 0.5 nm or more.
(通式(2)表示之化合物) 作為本態樣中使用之矽烷化劑之一例舉例為以下通式(2)表示之化合物。(Compound represented by general formula (2)) As an example of the silylating agent used in this aspect, the compound represented by the following general formula (2) is mentioned.
(上述通式(2)中,R4 、R5 及R6 分別獨立表示氫原子、含氮基或有機基,R4 、R5 及R6 所含之碳原子數之合計個數為1個以上,LG表示離去基)。 (In the above general formula (2), R 4 , R 5 and R 6 independently represent a hydrogen atom, a nitrogen-containing group or an organic group, and the total number of carbon atoms contained in R 4 , R 5 and R 6 is 1 more than one, LG means leaving group).
該通式(2)表示之化合物,使其構造中所含之離去基邊脫離邊與位於基板表面之官能基(典型上為-OH基、-NH2 基等)反應,可生成化學鍵。 作為該離去基,例示有例如通式(2)中之鍵結於矽原子之具有氮原子之含氮基或鹵基、通式(2)中之鍵結於矽原子之具有氧原子之醯氧基或硫氧基(sulfoxy)或該等之衍生物、氫原子、疊氮基。The compound represented by the general formula (2) reacts with a functional group (typically -OH group, -NH2 group, etc.) on the surface of the substrate while leaving the leaving group contained in its structure to form a chemical bond. As the leaving group, for example, a nitrogen-containing group or a halogen group having a nitrogen atom bonded to a silicon atom in the general formula (2), and a halogen group having an oxygen atom bonded to a silicon atom in the general formula (2) are exemplified. Acyloxy group or sulfoxyl group (sulfoxy group) or their derivatives, hydrogen atom, azido group.
作為上述通式(2)表示之具有取代基之化合物,更具體而言可使用下述通式(3)~(6)表示之化合物。As a compound which has a substituent represented by said general formula (2), the compound represented by following general formula (3)-(6) can be used more specifically.
(上述通式(3)中,R4 、R5 及R6 與上述通式(2)相同,R7 及R8 分別獨立表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或是飽和或不飽和雜環烷基,R7 及R8 亦可相互鍵結形成含氮原子之環構造,構成該環構造之環構成原子亦可包含氮原子以外之雜原子)。 (In the above general formula (3), R 4 , R 5 and R 6 are the same as the above general formula (2), R 7 and R 8 independently represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkane group, acetyl group, or saturated or unsaturated heterocycloalkyl group, R 7 and R 8 can also be bonded to each other to form a ring structure containing a nitrogen atom, and the ring constituent atoms constituting the ring structure can also include other than nitrogen atoms heteroatoms).
(上述通式(4)中,R4 、R5 及R6 與上述通式(2)相同,R9 表示氫原子、甲基、三甲基矽烷基或二甲基矽烷基,R10 、R11 及R12 分別獨立表示氫原子或有機基,R10 、R11 及R12 中所含之碳原子合計個數為1個以上)。 (In the above general formula (4), R 4 , R 5 and R 6 are the same as the above general formula (2), R 9 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R 10 , R 11 and R 12 each independently represent a hydrogen atom or an organic group, and the total number of carbon atoms contained in R 10 , R 11 and R 12 is 1 or more).
(上述通式(5)中,R4 、R5 及R6 與上述通式(2)相同,X表示O、CHR14 、CHOR14 、CR14 R14 或NR15 ,R13 及R14 分別獨立表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、三烷基矽烷基、三烷基矽氧基、烷氧基、苯基、苯基乙基或乙醯基,R15 表示氫原子、烷基或三烷基矽烷基)。 (In the above general formula (5), R 4 , R 5 and R 6 are the same as the above general formula (2), X represents O, CHR 14 , CHOR 14 , CR 14 R 14 or NR 15 , R 13 and R 14 are respectively independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trialkylsilyl group, a trialkylsilyloxy group, an alkoxy group, a phenyl group, a phenylethyl group or an acetyl group, R 15 represents a hydrogen atom, an alkyl group or a trialkylsilyl group).
(上述通式(6)中,R4 、R5 及R6 與上述通式(2)相同,R9 與上述通式(4)相同,R16 表示氫原子、飽和或不飽和烷基或三烷基矽烷基胺基)。 (In the above general formula (6), R 4 , R 5 and R 6 are the same as the above general formula (2), R 9 is the same as the above general formula (4), R 16 represents a hydrogen atom, a saturated or unsaturated alkyl group or trialkylsilylamino).
又,通式(3)~(6)中之烷基及環烷基亦可將於構成該烷基及環烷基之碳原子上鍵結之氫原子的一部分或全部藉由氟原子取代。In addition, the alkyl and cycloalkyl groups in the general formulas (3) to (6) may be substituted with fluorine atoms for part or all of the hydrogen atoms bonded to the carbon atoms constituting the alkyl and cycloalkyl groups.
作為上述通式(3)表示之化合物舉例為N,N-二甲基胺基三甲基矽烷、N,N-二甲基胺基二甲基矽烷、N,N-二甲基胺基單甲基矽烷、N,N-二乙基胺基三甲基矽烷、第三丁基胺基三甲基矽烷、烯丙基胺基三甲基矽烷、三甲基矽烷乙醯胺、N,N-二甲基胺基二甲基乙烯基矽烷、N,N-二甲基胺基二甲基丙基矽烷、N,N-二甲基胺基二甲基辛基矽烷、N,N-二甲基胺基二甲基苯基乙基矽烷、N,N-二甲基胺基二甲基苯基矽烷、N,N-二甲基胺基二甲基第三丁基矽烷、N,N-二甲基胺基三乙基矽烷、三甲基矽烷胺、單甲基矽烷基咪唑、二甲基矽烷基咪唑、三甲基矽烷基咪唑、單乙基矽烷基三唑、二甲基矽烷基三唑、三甲基矽烷基三唑、N-(三甲基矽烷基)二甲基胺、三甲基矽烷基嗎啉等。Examples of compounds represented by the above general formula (3) include N,N-dimethylaminotrimethylsilane, N,N-dimethylaminodimethylsilane, N,N-dimethylaminomono Methylsilane, N,N-diethylaminotrimethylsilane, tert-butylaminotrimethylsilane, allylaminotrimethylsilane, trimethylsilylacetamide, N,N -Dimethylaminodimethylvinylsilane, N,N-Dimethylaminodimethylpropylsilane, N,N-Dimethylaminodimethyloctylsilane, N,N-di Methylaminodimethylphenylethylsilane, N,N-Dimethylaminodimethylphenylsilane, N,N-Dimethylaminodimethylphenylethylsilane, N,N -Dimethylaminotriethylsilane, Trimethylsilylamine, Monomethylsilylimidazole, Dimethylsilylimidazole, Trimethylsilylimidazole, Monoethylsilyltriazole, Dimethylsilane Trimethylsilyl triazole, trimethylsilyl triazole, N-(trimethylsilyl) dimethylamine, trimethylsilyl morpholine, etc.
作為上述通式(4)表示之化合物舉例為六甲基二矽氮烷、N-甲基六甲基二矽氮烷、1,1,3,3-四甲基二矽氮烷、1,3-二甲基二矽氮烷、1,2-二-N-辛基四甲基二矽氮烷、1,2-二乙烯基四甲基二矽氮烷、七甲基二矽氮烷、九甲基三矽氮烷、參(二甲基矽烷基)胺、參(三甲基矽烷基)胺、五甲基乙基二矽氮烷、五甲基乙烯基二矽氮烷、五甲基丙基二矽氮烷、五甲基苯基乙基二矽氮烷、五甲基-第三丁基二矽氮烷、五甲基苯基二矽氮烷、三甲基三乙基二矽氮烷等。Examples of compounds represented by the above general formula (4) include hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1, 3-Dimethyldisilazane, 1,2-di-N-octyltetramethyldisilazane, 1,2-divinyltetramethyldisilazane, heptamethyldisilazane , nonamethyltrisilazane, ginseng (dimethylsilyl) amine, ginseng (trimethylsilyl) amine, pentamethylethyldisilazane, pentamethylvinyldisilazane, five Methylpropyldisilazane, pentamethylphenylethyldisilazane, pentamethyl-tert-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane Disilazane, etc.
作為上述通式(5)表示之矽烷化劑舉例為三甲基矽烷基乙酸酯、二甲基矽烷基乙酸酯、單甲基矽烷基乙酸酯、三甲基矽烷基丙酸酯、三甲基矽烷基丁酸酯、三甲基矽烷氧基-3-戊烯-2-酮等。Examples of the silylating agent represented by the above general formula (5) include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl propionate, Trimethylsilyl butyrate, trimethylsiloxy-3-penten-2-one, etc.
作為上述通式(6)表示之矽烷化劑舉例為雙(三甲基矽烷基)脲、N-三甲基矽烷基乙醯胺、N-甲基-N-三甲基矽烷基三氟乙醯胺等。Examples of the silylating agent represented by the above general formula (6) include bis(trimethylsilyl)urea, N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide Amide, etc.
上述各種化合物中,基於取得容易性或處理性高等之觀點,尤其較好使用通式(3)表示之化合物及通式(4)表示之化合物。Among the various compounds described above, the compound represented by the general formula (3) and the compound represented by the general formula (4) are particularly preferably used from the viewpoint of ease of acquisition and high handling properties.
又,上述通式(4)表示之化合物中,作為R4 及/或R10 具有氫原子之化合物亦為較佳之一例。 使用此等化合物時,認為化合物於基板上展開後,容易形成分子間之網絡。 亦有此等助益,一旦於基板上結合後,有即使加熱亦難以去除之傾向。藉此,如後所示,即使經表面處理之基板交付於原子層成長法等之高溫製程時,亦安定地保有矽烷基化部位。Moreover, among the compounds represented by the above-mentioned general formula (4), a compound having a hydrogen atom as R 4 and/or R 10 is also a preferable example. When these compounds are used, it is considered that an intermolecular network is easily formed after the compounds are spread out on the substrate. There are also these benefits. Once bonded on the substrate, it tends to be difficult to remove even if heated. Thereby, as shown below, even when the surface-treated substrate is delivered to a high-temperature process such as atomic layer growth, the silylation site is stably maintained.
又,上述通式(3)表示之化合物中,亦較好使用作為R5 具有含氮基、對於矽原子鍵結有2個氮原子之以下通式(3-a)表示之矽氮烷化合物。 使用此等化合物時,化合物中所含之2個氮原子分別對於基板上之官能基形成化學鍵。亦即,1個氮原子之2個鍵結鍵可結合於基板上,可於基板間形成更堅固之鍵。 再者,藉由可形成如此堅固之鍵,一旦於基板上結合後,亦有即使加熱亦難以去除之傾向。藉此,如後所示,即使經表面處理之基板交付於原子層成長法等之高溫製程時,亦安定地保有矽烷基化部位。 又,如以下定義,通式(3-a)中之R4 及R6 可為與通式(3)之R5 同樣之含氮基,對應於用途,亦可增強矽烷化劑與基板之相互作用。(上述通式(3-a)中,R4 及R6 分別獨立表示氫原子、含氮基或有機基,R4 及R6 中所含之碳原子合計之個數為1個以上,R7 、R8 、R17 、R18 分別表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或是飽和或不飽和雜環烷基,R7 及R8 或R17 及R18 亦可相互鍵結形成含氮原子之環構造,構成該環構造之環構成原子亦可含有氮原子以外之雜原子)。Also, among the compounds represented by the above-mentioned general formula (3), it is also preferable to use a silazane compound represented by the following general formula (3-a) having a nitrogen-containing group as R 5 and having two nitrogen atoms bonded to the silicon atom . When these compounds are used, the two nitrogen atoms contained in the compounds respectively form chemical bonds with the functional groups on the substrate. That is, two bonding bonds of one nitrogen atom can be bonded to the substrate, and a stronger bond can be formed between the substrates. Furthermore, since such a strong bond can be formed, once bonded on the substrate, it tends to be difficult to remove even by heating. Thereby, as will be shown later, even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth, the silylation site is stably maintained. Also, as defined below, R 4 and R 6 in the general formula (3-a) can be the same nitrogen-containing group as R 5 of the general formula (3), which can also enhance the bonding between the silylation agent and the substrate according to the application. interaction. (In the above general formula (3-a), R 4 and R 6 independently represent a hydrogen atom, a nitrogen-containing group or an organic group, the total number of carbon atoms contained in R 4 and R 6 is 1 or more, and R 7 , R 8 , R 17 , and R 18 respectively represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an acetyl group, or a saturated or unsaturated heterocycloalkyl group, R 7 and R 8 Alternatively, R 17 and R 18 may be bonded to each other to form a ring structure containing a nitrogen atom, and the ring constituting atoms constituting the ring structure may also contain heteroatoms other than nitrogen atoms).
又,若關注於鍵結於矽原子之取代基,較好使用該取代基所含之碳原子數之較大的所謂巨大(體積大)取代基鍵結於矽原子之矽烷化劑。藉由表面處理劑含有此等矽烷化劑,藉由該表面處理劑可增大接受處理之基板表面之疏水性。藉此,可選擇性提高基板表面之材質不同的2種以上之鄰接區域間的疏水性提高。Also, when focusing on a substituent bonded to a silicon atom, it is preferable to use a so-called bulky (bulky) silylating agent in which the number of carbon atoms contained in the substituent is bonded to a silicon atom. By containing such a silanizing agent in the surface treatment agent, the hydrophobicity of the surface of the substrate to be treated can be increased by the surface treatment agent. Thereby, the improvement of hydrophobicity between two or more types of adjacent regions having different materials on the surface of the substrate can be selectively enhanced.
因此,上述通式(2)中,R4 、R5 及R6 所含之碳原子合計個數較好為3個以上。其中,基於於矽烷化反應中獲得充分反應性之觀點,更好為上述通式(2)中,R4 、R5 及R6 係任一者為碳原子數2個以上之有機基(以下該段落中,稱為「特定有機基」),其餘2個分別獨立為甲基或乙基。作為特定有機基,例示為可具有分支及/或取代基之碳原子數2以上20以下之烷基、可具有取代基之乙烯基、可具有取代基之芳基等。特定有機基之碳原子數更好為2以上12以下,又更好為2以上10以下,特佳為2以上8以下。Therefore, in the above general formula (2), the total number of carbon atoms contained in R 4 , R 5 and R 6 is preferably 3 or more. Among them, based on the viewpoint of obtaining sufficient reactivity in the silylation reaction, it is more preferable that in the above general formula (2), any one of R 4 , R 5 and R 6 is an organic group with 2 or more carbon atoms (hereinafter In this paragraph, referred to as "specific organic group"), and the remaining two are independently methyl or ethyl. Examples of the specific organic group include an alkyl group having 2 to 20 carbon atoms which may have a branch and/or a substituent, a vinyl group which may have a substituent, an aryl group which may have a substituent, and the like. The number of carbon atoms in the specific organic group is more preferably from 2 to 12, still more preferably from 2 to 10, particularly preferably from 2 to 8.
基於此等觀點,上述例示之通式(2)表示之具有取代基之矽烷化劑中,較好例示N,N-二甲基胺基二甲基乙烯基矽烷、N,N-二甲基胺基二甲基丙基矽烷、N,N-二甲基胺基二甲基辛基矽烷、N,N-二甲基胺基二甲基苯基乙基矽烷、N,N-二甲基胺基二甲基苯基矽烷、N,N-二甲基胺基二甲基第三丁基矽烷、N,N-二甲基胺基三乙基矽烷、N,N-二甲基胺基三甲基矽烷等。Based on these viewpoints, among the silylating agents with substituents represented by the general formula (2) exemplified above, N,N-dimethylaminodimethylvinylsilane, N,N-dimethyl Aminodimethylpropylsilane, N,N-Dimethylaminodimethyloctylsilane, N,N-Dimethylaminodimethylphenylethylsilane, N,N-Dimethyl Aminodimethylphenylsilane, N,N-Dimethylaminodimethyltert-butylsilane, N,N-Dimethylaminotriethylsilane, N,N-Dimethylamino Trimethylsilane, etc.
(環狀矽氮烷) 作為環狀矽氮烷化合物,舉例為2,2,5,5-四甲基-2,5-二矽雜-1-氮雜環戊烷、2,2,6,6-四甲基-2,6-二矽雜-1-氮雜環己烷等之環狀二矽氮烷化合物;2,2,4,4,6,6-六甲基環三矽氮烷、2,4,6-三甲基-2,4,6-三乙烯基環三矽氮烷等之環狀三矽氮烷化合物;2,2,4,4,6,6,8,8-八甲基環四矽氮烷等之環狀四矽氮烷化合物;等。 此等環狀矽氮烷化合物中,可較好地使用具有對於1個矽原子鍵結2個以上含氮基之部分構造的化合物。該情況,與前述通式(3-a)同樣,可於矽烷化劑與基板間形成更堅固結合,一旦基板上結合後,有即使加熱亦難以去除之傾向。藉此,如後所示,即使經表面處理之基板交付於原子層成長法等之高溫製程時,亦安定地保有矽烷化部位。(Cyclic silazane) Examples of cyclic silazane compounds include 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,6 , Cyclic disilazane compounds such as 6-tetramethyl-2,6-disila-1-azacyclohexane; 2,2,4,4,6,6-hexamethylcyclotrisil Cyclic trisilazane compounds such as azane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; 2,2,4,4,6,6,8 , Cyclic tetrasilazane compounds such as 8-octamethylcyclotetrasilazane; etc. Among these cyclic silazane compounds, compounds having a partial structure in which two or more nitrogen-containing groups are bonded to one silicon atom can be preferably used. In this case, similar to the aforementioned general formula (3-a), a stronger bond can be formed between the silylation agent and the substrate, and once bonded to the substrate, it tends to be difficult to remove even by heating. Thereby, as will be shown later, even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth, the silanization site is stably maintained.
(其他矽烷化劑) 上述化合物以外,亦可使用下述通式(7)、(8)或(9)表示之化合物作為矽烷化劑。(Other silylating agents) In addition to the above compounds, compounds represented by the following general formula (7), (8) or (9) can also be used as silylating agents.
(上述通式(7)中,R19 及R20 分別獨立表示氫原子、烷基、三烷基矽烷基,R19 及R20 之至少1個表示三烷基矽烷基,且R21 表示氫原子之一部分或全部可藉由氟原子取代之碳原子數1以上10以下之脂肪族烴基)。 (In the above general formula (7), R 19 and R 20 independently represent a hydrogen atom, an alkyl group, and a trialkylsilyl group, at least one of R 19 and R 20 represents a trialkylsilyl group, and R 21 represents a hydrogen atom An aliphatic hydrocarbon group having 1 to 10 carbon atoms in which some or all of the atoms may be substituted by fluorine atoms).
(上述通式(8)中,R22 表示三烷基矽烷基,R23 及R24 分別獨立表示氫原子或有機基)。 (In the above general formula (8), R 22 represents a trialkylsilyl group, and R 23 and R 24 independently represent a hydrogen atom or an organic group).
(上述通式(9)中,R4 、R5 及R6 與上述通式(2)同樣,R25 表示單鍵或有機基,R26 不存在,或於存在時,表示-SiR27 R28 R29 ,R27 、R28 及R29 分別獨立表示氫原子、含氮基或有機基)。 (In the above general formula (9), R 4 , R 5 and R 6 are the same as the above general formula (2), R 25 represents a single bond or an organic group, R 26 does not exist, or when present, it represents -SiR 27 R 28 R 29 , R 27 , R 28 and R 29 each independently represent a hydrogen atom, a nitrogen-containing group or an organic group).
作為上述式(7)表示之化合物,舉例為雙(三甲基矽烷基)三氟乙醯胺、三甲基矽烷基甲基乙醯胺、雙三甲基矽烷基乙醯胺等,作為上述通式(8)表示之化合物舉例為2-三甲基矽氧基戊-2-烯-4-酮等。作為上述式(9)表示之化合物舉例為1,2-雙(二甲基氯矽烷基)乙烷、第三丁基二甲基氯矽烷等。Examples of the compound represented by the above formula (7) include bis(trimethylsilyl)trifluoroacetamide, trimethylsilylmethylacetamide, bistrimethylsilylacetamide, etc., as the above-mentioned The compound represented by the general formula (8) is exemplified by 2-trimethylsiloxypent-2-en-4-one and the like. Examples of the compound represented by the above formula (9) include 1,2-bis(dimethylchlorosilyl)ethane, tert-butyldimethylchlorosilane, and the like.
上述例示之矽烷化劑可單獨使用或混合2種以上使用。The above exemplified silylation agents may be used alone or in combination of two or more.
作為上述表面處理劑之矽烷化劑(A)之含量,只要未損及本發明效果則未特別限制,較好相對於上述表面處理劑總量為0.001質量%以上,更好為0.01質量%以上,又更好為0.1質量%以上,特佳為0.5質量%以上,最好為1.0質量%以上。 作為上述表面處理劑之矽烷化劑(A)之含量的上限值,只要不損及本發明效果則未特別限制,但可為例如30質量%以下、15質量%以下、10質量%以下,典型上為8質量%以下。The content of the silanizing agent (A) as the above-mentioned surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably at least 0.001% by mass, more preferably at least 0.01% by mass, based on the total amount of the above-mentioned surface treatment agent , more preferably at least 0.1% by mass, particularly preferably at least 0.5% by mass, most preferably at least 1.0% by mass. The upper limit of the content of the silanizing agent (A) in the surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but it may be, for example, 30% by mass or less, 15% by mass or less, or 10% by mass or less, Typically, it is 8 mass % or less.
[含氮雜環化合物(B)] 表面處理劑包含含氮雜環化合物(B)。 藉由使表面處理劑包含含氮雜環化合物(B),可促進矽烷化劑之矽烷化反應、上述烷氧基單矽烷化合物之水解乃至縮合、對基板表面之結合,藉由自基板表面存在之羥基脫除氫而可使該基板表面活性化,其結果,可選擇性提高基板表面之材質不同的2個以上之鄰接區域間之疏水性。[Nitrogen-Containing Heterocyclic Compound (B)] The surface treatment agent contains a nitrogen-containing heterocyclic compound (B). By including the nitrogen-containing heterocyclic compound (B) in the surface treatment agent, the silylation reaction of the silylation agent, the hydrolysis and condensation of the above-mentioned alkoxymonosilane compound, and the bonding to the substrate surface can be promoted. The surface of the substrate can be activated by dehydrogenation of the hydroxyl group, and as a result, the hydrophobicity between two or more adjacent regions of different materials on the surface of the substrate can be selectively increased.
含氮雜環化合物(B)若為環構造中含有氮原子之化合物則未特別限定,但基於選擇性提高基板表面之材質不同的2個以上之鄰接區域間之疏水性之觀點,氮原子較好含2個以上5個以下,更好含2個以上4個以下,又更好含2個或3個。 含氮雜環化合物(B)於環中亦可含有氧原子、硫原子等之氮原子以外之雜原子。含氮雜環化合物(B)典型上可採用其構造中不含矽原子之化合物。 含氮雜環化合物(B),基於表面疏水化之觀點,較好為含有具有芳香性的含氮雜環之化合物。The nitrogen-containing heterocyclic compound (B) is not particularly limited as long as it is a compound containing a nitrogen atom in the ring structure, but from the viewpoint of selectively improving the hydrophobicity between two or more adjacent regions having different materials on the surface of the substrate, the nitrogen atom is more Preferably more than 2 and less than 5, more preferably more than 2 and less than 4, more preferably 2 or 3. The nitrogen-containing heterocyclic compound (B) may also contain heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms in the ring. As the nitrogen-containing heterocyclic compound (B), typically, a compound that does not contain a silicon atom in its structure can be used. The nitrogen-containing heterocyclic compound (B) is preferably a compound containing an aromatic nitrogen-containing heterocyclic ring from the viewpoint of surface hydrophobization.
含氮雜環化合物(B)可為2個以上之複數環以單鍵或2價以上之多價連結基鍵結之化合物。該情況下,藉由連結基鍵結之2個以上之複數環只要含有至少一個含氮雜環即可。 多價連結基中,基於環彼此之立體障礙較小之觀點較好為2價連結基。作為2價連結基之具體例,舉例為碳原子數1以上6以下之伸烷基、-CO-、-CS-、-O-、-S-、-NH-、-N=N-、 -CO-O-、-CO-NH-、-CO-S-、-CS-O-、-CS-S-、-CO-NH-CO-、-NH-CO-NH-、-SO-及-SO2 -等。 2個以上之複數環藉由多價連結基鍵結之化合物中所含之環數,基於容易調製均一表面處理劑之方面,較好為4以下,更好為3以下,最好為2。又,例如於如萘環之縮合環,環數設為2。The nitrogen-containing heterocyclic compound (B) may be a compound in which two or more plural rings are bonded by a single bond or a polyvalent linking group having a valence of two or more. In this case, two or more plural rings bonded via a linking group need only contain at least one nitrogen-containing heterocycle. Among the polyvalent linking groups, a divalent linking group is preferred from the viewpoint that the steric barrier between the rings is small. Specific examples of divalent linking groups include alkylene groups having 1 to 6 carbon atoms, -CO-, -CS-, -O-, -S-, -NH-, -N=N-, - CO-O-, -CO-NH-, -CO-S-, -CS-O-, -CS-S-, -CO-NH-CO-, -NH-CO-NH-, -SO- and - SO 2 -etc. The number of rings contained in the compound in which two or more plural rings are bonded by a polyvalent linking group is preferably at most 4, more preferably at most 3, most preferably 2, from the viewpoint of ease of preparation of a uniform surface treatment agent. Also, for example, in a condensed ring such as a naphthalene ring, the number of rings is two.
含氮雜環化合物(B)亦可為2個以上之複數環經縮合之含氮雜環化合物。該情況下,只要構成縮合環之環中之至少一個環為含氮雜環即可。 2個以上之複數環經縮合之含氮雜環化合物中所含之環數,基於容易調製均一表面處理劑之方面,較好為4以下,更好為3以下,最好為2。The nitrogen-containing heterocyclic compound (B) may be a nitrogen-containing heterocyclic compound in which two or more plural rings are condensed. In this case, at least one of the rings constituting the condensed ring should just be a nitrogen-containing heterocyclic ring. The number of rings contained in the nitrogen-containing heterocyclic compound having condensed plural rings of two or more rings is preferably at most 4, more preferably at most 3, most preferably at most 2, in view of the ease of preparation of a uniform surface treatment agent.
基於表面疏水化之觀點,含氮雜環化合物(B)較好含有含氮5員環或包含含氮5員環骨架之縮合多環。From the viewpoint of surface hydrophobization, the nitrogen-containing heterocyclic compound (B) preferably contains a nitrogen-containing 5-membered ring or a condensed polycyclic ring including a nitrogen-containing 5-membered ring skeleton.
作為含氮雜環化合物(B)中所含之含氮雜環較好為可具有取代基之咪唑、可具有取代基之三唑、可具有取代基之四唑、可具有取代基之苯并三唑或可具有取代基之吡唑,更好為選自由可具有取代基之咪唑、可具有取代基之三唑及可具有取代基之四唑所組成之群中之一種以上。The nitrogen-containing heterocycle contained in the nitrogen-containing heterocyclic compound (B) is preferably imidazole which may have a substituent, triazole which may have a substituent, tetrazole which may have a substituent, and benzo which may have a substituent. Triazole or optionally substituted pyrazole, more preferably one or more selected from the group consisting of optionally substituted imidazole, optionally substituted triazole, and optionally substituted tetrazole.
作為上述取代基,舉例為碳原子數1以上6以下之烷基、碳原子數3以上8以下之環烷基、碳原子數1以上6以下之烷氧基、碳原子數3以上8以下之環烷氧基、碳原子數6以上20以下之芳基、碳原子數7以上20以下之芳烷基、碳原子數1以上6以下之鹵化烷基、碳原子數2以上7以下之脂肪族醯基、碳原子數2以上7以下之鹵化脂肪族醯基、碳原子數7以上20以下之芳羰基、碳原子數2以上7以下之羧基烷基、鹵原子、羥基、巰基、碳原子數1以上6以下之烷硫基、胺基、含有碳原子數1以上6以下之烷基的單烷胺基、含有碳原子數1以上6以下之烷基的二烷胺基、硝基及氰基。 含氮雜環化合物(B)可於雜環上可具有複數個取代基。取代基數為複數個時,複數個取代基可相同亦可不同。 該等取代基包含脂肪族烴環或芳香族烴環等時,該等環可進而具有與含氮雜環化合物(B)可具有之取代基相同的取代基。Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 3 to 8 carbon atoms. Cycloalkoxy group, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, halogenated alkyl group with 1 to 6 carbon atoms, aliphatic group with 2 to 7 carbon atoms Acyl group, halogenated aliphatic acyl group with 2 to 7 carbon atoms, arylcarbonyl group with 7 to 20 carbon atoms, carboxyalkyl group with 2 to 7 carbon atoms, halogen atom, hydroxyl group, mercapto group, carbon number Alkylthio groups of 1 to 6, amino groups, monoalkylamino groups containing alkyl groups with 1 to 6 carbon atoms, dialkylamino groups with alkyl groups with 1 to 6 carbon atoms, nitro groups and cyano groups base. The nitrogen-containing heterocyclic compound (B) may have multiple substituents on the heterocyclic ring. When the number of substituents is plural, the plural substituents may be the same or different. When these substituents include aliphatic hydrocarbon rings or aromatic hydrocarbon rings, etc., these rings may further have the same substituents as the nitrogen-containing heterocyclic compound (B) may have.
作為雜環化合物之特佳具體例舉例為下式化合物。Particularly preferred specific examples of the heterocyclic compound include compounds of the following formulae.
上述表面處理劑中之含氮雜環化合物(B)含量只要不損及本發明效果則未特別限制,相對於上述表面處理劑總量,較好為0.001質量%以上,更好為0.01質量%以上,又更好為0.1質量%以上,特佳為0.5質量%以上,最好為1.0質量%以上。 作為上述表面處理劑中之上述含氮雜環化合物(B)含量之上限值只要不損及本發明效果則未特別限制,但可為例如30質量%以下、15質量%以下、10質量%以下,典型上為5質量%以下。The content of the nitrogen-containing heterocyclic compound (B) in the surface treatment agent is not particularly limited as long as it does not impair the effect of the present invention, and is preferably at least 0.001% by mass, more preferably 0.01% by mass, based on the total amount of the surface treatment agent or more, more preferably at least 0.1% by mass, particularly preferably at least 0.5% by mass, most preferably at least 1.0% by mass. The upper limit of the nitrogen-containing heterocyclic compound (B) content in the surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but may be, for example, 30% by mass or less, 15% by mass or less, or 10% by mass Below, typically 5% by mass or less.
[溶劑] 藉由表面處理劑含有溶劑,基於利用浸漬法、旋轉塗佈法等之基板表面處理之容易性的觀點,表面處理劑較好含有溶劑。[Solvent] Since the surface treatment agent contains a solvent, it is preferable that the surface treatment agent contains a solvent from the viewpoint of easiness of substrate surface treatment by a dipping method, a spin coating method, or the like.
作為溶劑之具體例舉例為二甲基亞碸等之亞碸類; 二甲基碸、二乙基碸、雙(2-羥基乙基)碸、四亞甲基碸等之碸類; N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等之醯胺類; N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-丙基-2-吡咯啶酮、N-羥基甲基-2-吡咯啶酮、N-羥基乙基-2-吡咯啶酮等之內醯胺類; 1,3-二甲基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、1,3-二異丙基-2-咪唑啶酮等之咪唑啶酮類; 二甲基甘醇、二乙基二甘醇、二甲基三甘醇、甲基乙基二甘醇、二乙基甘醇、三乙二醇丁基甲基醚等之二烷基甘醇醚類; 甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、正戊醇、異戊醇、2-甲基丁醇、第二戊醇、第三戊醇、3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、正己醇、2-甲基戊醇、第二己醇、2-乙基丁醇、第二庚醇、3-庚醇、正辛醇、2-乙基己醇、第二辛醇、正壬醇、2,6-二甲基-4-庚醇、正癸醇、第二-十一烷醇、三甲基壬醇、第二-十四烷醇、第二-十七烷醇、苯酚、環己醇、甲基環己醇、3,3,5-三甲基環己醇、苄醇、苯基甲基卡必醇、二丙酮醇、甲酚等之單醇系溶劑; 乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等之(聚)烷二醇單烷醚類; 乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等之(聚)烷二醇單烷醚乙酸酯類; 二甲醚、二乙醚、甲基乙基醚、二丙醚、二異丙醚、二丁醚、二異戊醚、二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚、四乙二醇二甲醚、四氫呋喃等之其他醚類; 甲基乙基酮、環己酮、2-庚酮、3-庚酮等之酮類; 2-羥基丙酸甲酯、2-羥基丙酸乙酯等之乳酸烷酯類;2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基-1-丁酯、丙酸3-甲基-3-甲氧基丁酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸正己酯、乙酸正庚酯、乙酸正辛酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、正辛酸甲酯、癸酸甲酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯、己二酸二甲酯、丙二醇二乙酸酯等之其他酯類; β-丙內酯、γ-丁內酯、δ-戊內酯等之內酯類; 正己烷、正庚烷、正辛烷、正壬烷、甲基辛烷、正癸烷、正十一烷、正十二烷、2,2,4,6,6-五甲基庚烷、2,2,4,4,6,8,8-七甲基壬烷、環己烷、甲基環己烷等之直鏈狀、分支鏈狀或環狀之脂肪族烴類; 苯、甲苯、二甲苯、1,3,5-三甲基苯、萘等之芳香族烴類; 對-薄荷烷、二苯基薄荷烷、檸檬烯、萜品烯、冰片烷、降冰片烷、蒎烷等之萜烯類;等。該等溶劑可單獨使用或混合2種以上使用。Specific examples of solvents include dimethylphenoxide, etc.; dimethylsulfide, diethylsulfone, bis(2-hydroxyethyl)sulfone, tetramethylenesulfone, etc.; N, Amides of N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide, etc. Class; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxy Lactamides such as ethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl imidazolidinones such as 2-imidazolidinone; Dimethyl glycol, diethyl diethylene glycol, dimethyl triethylene glycol, methyl ethyl diethylene glycol, diethyl glycol, triethyl glycol Dialkyl glycol ethers such as glycol butyl methyl ether; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, Pentanol, 2-methylbutanol, 2-pentanol, 3-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol , second hexanol, 2-ethylbutanol, second heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl -4-heptanol, n-decyl alcohol, second-undecanol, trimethylnonanol, second-tetradecanol, second-heptadecanol, phenol, cyclohexanol, methylcyclohexyl alcohol Monoalcohol solvents such as alcohol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbitol, diacetone alcohol, and cresol; Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc. Diethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) alkylene glycol monoalkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (poly) alkylene glycol monoalkyl ether acetates; Dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol di Methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran and other ethers; Methyl ethyl ketone, cyclohexanone, 2-heptanone, Ketones such as 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and 3-methoxypropionate Methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy- Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, 3-methyl-3-methoxybutyl propionate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, isoacetic acid Amyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl caprate, methyl pyruvate, ethyl pyruvate Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, dimethyl adipate, propylene glycol diacetate, etc.; Lactones, γ-butyrolactone, δ-valerolactone and other lactones; n-hexane, n-heptane, n-octane, n-nonane, methyl octane, n-decane, n-undecane, n- Dodecane, 2,2,4,6,6-pentamethylheptane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, methylcyclohexane, etc. straight-chain, branched-chain or cyclic aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene, etc.; p-menthane, diphenyl Terpenes such as menthane, limonene, terpinene, bornane, norbornane, pinane, etc.; etc. These solvents can be used individually or in mixture of 2 or more types.
上述溶劑中,較好為可溶解矽烷化劑(A)及含氮雜環化合物(B),且對於基板表面(有機圖型、無機圖型等)之損傷較少的溶劑。 作為溶劑,基於可溶解矽烷化劑(A)及含氮雜環化合物(B)兩者且選擇性提高基板表面之材質不同的2個以上鄰接區域間之疏水性之觀點,較好為介電率1以上25以下之溶劑,更好為介電率2以上20以下之溶劑,更好為介電率3以上15以下之溶劑,特佳為介電率4以上10以下之溶劑,最好為介電率5以上8以下之溶劑。Among the above-mentioned solvents, solvents that can dissolve the silylation agent (A) and the nitrogen-containing heterocyclic compound (B) and cause less damage to the surface of the substrate (organic patterns, inorganic patterns, etc.) are preferred. As a solvent, a dielectric is preferable from the viewpoint of dissolving both the silylation agent (A) and the nitrogen-containing heterocyclic compound (B) and selectively improving the hydrophobicity between two or more adjacent regions of different substrate surface materials. Solvents with a dielectric ratio of 1 to 25, more preferably solvents with a dielectric ratio of 2 to 20, more preferably solvents with a dielectric ratio of 3 to 15, particularly preferably solvents with a dielectric ratio of 4 to 10, most preferably Solvents with a dielectric ratio of 5 to 8.
作為滿足上述介電率之溶劑,較好為乙酸3-甲基-3-甲氧基-1-丁酯、乙酸乙酯、丙二醇單甲醚乙酸酯、丙二醇單甲醚、二乙二醇單甲醚、異丙醇或甲基乙基酮,更好為乙酸3-甲基-3-甲氧基-1-丁酯、乙酸乙酯或丙二醇單甲醚乙酸酯。As a solvent satisfying the above dielectric ratio, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol Monomethyl ether, isopropanol or methyl ethyl ketone, more preferably 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate or propylene glycol monomethyl ether acetate.
<<對基板上之區域選擇性製膜方法>> 其次,針對使用第1態樣之表面處理方法對基板上區域選擇性製膜方法加以說明。 本態樣中,對基板上之區域選擇性製膜方法係包含 藉由上述第1態樣之表面處理方法,處理上述基板之上述表面;及 於經表面處理之上述基板之表面藉由ALD法形成膜, 使上述膜之材料堆積量區域選擇性地不同。<<Regioselective film formation method on the substrate>> Next, the method of regioselective film formation on the substrate using the surface treatment method of the first aspect will be described. In this aspect, the region-selective film-forming method on the substrate includes treating the above-mentioned surface of the above-mentioned substrate by the surface treatment method of the above-mentioned first aspect; Membranes, making the material accumulation amount of the above-mentioned membranes regionally different selectively.
以上述第1態樣之方法之表面處理結果,使上述2個以上區域間之水的接觸角(較好為疏水性)成為不同,本發明中,可使上述2個以上區域間之形成上述膜之材料的堆積量於基板表面之區域選擇性不同。 具體而言,較好於上述2個以上區域間之水的接觸角(較好為疏水性)於較其他區域更大之區域,利用ALD法之膜形成材料難以吸附(較好為化學性吸附)於基板表面之上述區域,而於上述2個以上區域間之膜形成材料之堆積量產生差異之結果,使基板上之區域選擇性膜形成材料的堆積量不同。 作為上述化學吸附,舉例為與羥基之化學吸附等。As a result of the surface treatment of the method of the above-mentioned first aspect, the contact angle of water (preferably hydrophobicity) between the above-mentioned two or more regions becomes different. In the present invention, the formation of the above-mentioned The accumulation amount of the material of the film is different according to the region selectivity of the surface of the substrate. Specifically, the contact angle of water between the above two or more regions is better (preferably hydrophobic) in a region larger than the other regions, and the film forming material by ALD method is difficult to adsorb (preferably chemical adsorption) ) in the aforementioned regions on the surface of the substrate, and as a result of differences in the deposited amount of the film-forming material between the above-mentioned two or more regions, the deposited amount of the regioselective film-forming material on the substrate is different. Examples of the above-mentioned chemical adsorption include chemical adsorption with hydroxyl groups and the like.
上述2個以上之區域間,作為水的接觸角(較好為疏水性)較其他區域大之傾向之區域,舉例為包含自Si、SiN、Ox、TiN、TaN、Ge及SiGe所組成之群中選擇之至少1種的區域。 上述2個以上之區域間,作為水的接觸角(較好為疏水性)較其他區域小的傾向之區域,舉例為包含自W、Co、Al、Ni、Ru、Cu、TiN及TaN所組成之群中選擇之至少1種的區域。Between the above two or more regions, the region where the contact angle of water (preferably hydrophobicity) tends to be larger than the other regions is, for example, a group consisting of Si, SiN, Ox, TiN, TaN, Ge, and SiGe An area of at least one of the selected ones. Between the above two or more regions, as a region where the contact angle of water (preferably hydrophobicity) tends to be smaller than that of other regions, for example, it is composed of W, Co, Al, Ni, Ru, Cu, TiN, and TaN. An area of at least one selected from the group.
(藉由ALD法之膜形成) 作為藉由ALD法之膜形成方法並未特別限制,但較好為藉由使用至少2種氣相反應物質(以下簡稱為「前驅物氣體」)之吸附(較好為化學吸附)之薄膜形成方法。 具體而言,舉例為包含下述步驟(a)及(b),重複至少1次(1循環)下述步驟(a)及(b)直至獲得期望膜厚之方法等。 (a)將以上述第1態樣之方法表面處理之基板暴露於第1前驅物氣體之脈衝中之步驟,及 (b)於上述步驟(a)之後,將基板暴露於第2前驅物氣體之脈衝中之步驟。(Film Formation by ALD Method) The film formation method by ALD method is not particularly limited, but it is preferably adsorption ( Preferably, it is a film forming method of chemical adsorption). Specifically, a method including the following steps (a) and (b) and repeating the following steps (a) and (b) at least once (1 cycle) until a desired film thickness is obtained is exemplified. (a) a step of exposing the substrate surface-treated by the method of the first aspect above to pulses of the first precursor gas, and (b) after the above step (a), exposing the substrate to the second precursor gas steps in the pulse.
上述步驟(a)之後且上述步驟(b)之前,亦可包含電漿處理步驟、藉由載氣、第2前驅物氣體等去除或排氣(吹拂)掉第1前驅物氣體及其反應物之步驟等,亦可不含該等步驟。 上述步驟(b)之後,亦可包含電漿處理步驟、藉由載氣等去除或排氣掉第2前驅物氣體及其反應物之步驟等,亦可不含該等步驟。 作為載氣,舉例為氮氣、氬氣、氦氣等之惰性氣體。After the above step (a) and before the above step (b), it may also include a plasma treatment step, removing or exhausting (blowing) the first precursor gas and its reactants by carrier gas, second precursor gas, etc. steps, etc., may not include these steps. After the above step (b), the step of plasma treatment, the step of removing or degassing the second precursor gas and its reactants by means of carrier gas, etc. may also be included, or these steps may not be included. Examples of carrier gas include inert gases such as nitrogen, argon, and helium.
較好每個各循環之各脈衝及形成之各層係自我控制,更好所形成之各層為單原子層。 作為上述單原子層之膜厚,可為例如5nm以下,較好為3nm以下,更好為1nm以下,又更好為0.5nm以下。Preferably the pulses of each cycle and the layers formed are self-controlled, more preferably the layers formed are monoatomic layers. The film thickness of the monoatomic layer is, for example, not more than 5 nm, preferably not more than 3 nm, more preferably not more than 1 nm, more preferably not more than 0.5 nm.
作為第1前驅物氣體,舉例為有機金屬、金屬鹵化物、金屬氧化鹵化物等,具體而言,舉例為五乙氧化鉭、肆(二甲胺基)鈦、伍(二甲胺基)鉭、肆(二甲胺基)鋯、肆(二甲胺基)鉿、肆(二甲胺基)矽烷、六氟乙醯丙酮銅乙烯基三甲基矽烷、Zn(C2 H5 )2 、Zn(C2 H5 )2 、Zn(CH3 )2 、TMA(三甲基鋁)、TaCl5 、WF6 、WOCl4 、CuCl、ZrCl4 、AlCl3 、TiCl4 、SiCl4 、HfCl4 等。Examples of the first precursor gas include organic metals, metal halides, and metal oxide halides, and specifically, tantalum pentaethoxide, tetrakis(dimethylamino)titanium, and pentano(dimethylamino)tantalum , Si(dimethylamino)zirconium, Si(dimethylamino)hafnium, Si(dimethylamino)silane, copper hexafluoroacetylacetonate vinyltrimethylsilane, Zn(C 2 H 5 ) 2 , Zn(C 2 H 5 ) 2 , Zn(CH 3 ) 2 , TMA (trimethylaluminum), TaCl 5 , WF 6 , WOCl 4 , CuCl, ZrCl 4 , AlCl 3 , TiCl 4 , SiCl 4 , HfCl 4 , etc. .
作為第2前驅物氣體舉例為可分解第1前驅物之前驅物氣體或可去除第1前驅物之配位子的前驅物氣體,具體舉例為H2 O、H2 O2 、O2 、O3 、NH3 、H2 S、H2 Se、PH3 、AsH3 、C2 H4 或Si2 H6 等。The second precursor gas is, for example, a precursor gas that can decompose the first precursor or a precursor gas that can remove the ligand of the first precursor. Specific examples are H 2 O, H 2 O 2 , O 2 , O 3. NH 3 , H 2 S, H 2 Se, PH 3 , AsH 3 , C 2 H 4 or Si 2 H 6 etc.
作為步驟(a)之暴露溫度並未特別限制,例如為100℃以上800℃以下,較好為150℃以上650℃以下,更好為200℃以上500℃以下,又更好為225℃以上375℃以下。The exposure temperature of the step (a) is not particularly limited, for example, it is 100°C to 800°C, preferably 150°C to 650°C, more preferably 200°C to 500°C, and more preferably 225°C to 375°C. below ℃.
作為步驟(b)之暴露溫度並未特別限制,舉例為與步驟(a)中之暴露溫度實質相等或其以上之溫度。The exposure temperature in the step (b) is not particularly limited, and is, for example, a temperature substantially equal to or higher than the exposure temperature in the step (a).
作為藉由ALD法形成的膜並未特別限制,舉例為含純元素之膜(例如Si、Cu、Ta、W)、含氧化物之膜(例如SiO2 、GeO2 、HfO2 、ZrO2 、Ta2 O5 、TiO2 、Al2 O3 、ZnO、SnO2 、Sb2 O5 、B2 O3 、In2 O3 、WO3 )、含氮化物之膜(例如Si3 N4 、TiN、AlN、BN、GaN、NbN)、含碳化物之膜(例如SiC)、含硫化物之膜(例如CdS、ZnS、MnS、WS2 、PbS)、含硒化物之膜(例如CdSe、ZnSe)、含磷化物之膜(GaP、InP)、含砷化物之膜(例如GaAs、InAs)或該等之混合物等。 [實施例]The film formed by the ALD method is not particularly limited, and examples include films containing pure elements (such as Si, Cu, Ta, W), films containing oxides (such as SiO 2 , GeO 2 , HfO 2 , ZrO 2 , Ta 2 O 5 , TiO 2 , Al 2 O 3 , ZnO, SnO 2 , Sb 2 O 5 , B 2 O 3 , In 2 O 3 , WO 3 ), films containing nitrides (such as Si 3 N 4 , TiN , AlN, BN, GaN, NbN), carbide-containing film (such as SiC), sulfide-containing film (such as CdS, ZnS, MnS, WS 2 , PbS), selenide-containing film (such as CdSe, ZnSe) , phosphide-containing film (GaP, InP), arsenide-containing film (such as GaAs, InAs) or a mixture thereof, etc. [Example]
以下顯示實施例進一步具體說明本發明,但本發明之範圍並非限定於該等實施例者。The following examples are shown to further describe the present invention in detail, but the scope of the present invention is not limited to these examples.
[實施例1~4及比較例1] (表面處理劑之調製) 於溶劑乙酸3-甲基-3-甲氧基-1-丁酯(MMBA)中,均一混合矽烷化劑(A)的正辛基三甲氧基矽烷7.8質量%與下述表1中記載之含氮雜環化合物(B)(以下亦簡稱為「化合物(B)」) 1.0質量%,調製實施例1~4及比較例1的表面處理劑。[Examples 1 to 4 and Comparative Example 1] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate (MMBA), uniformly mix the silylating agent (A) 7.8% by mass of n-octyltrimethoxysilane and 1.0% by mass of the nitrogen-containing heterocyclic compound (B) (hereinafter also referred to as "compound (B)") listed in Table 1 below to prepare Examples 1 to 4 and compare The surface treatment agent of Example 1.
(表面處理) 使用所得之實施例1~4及比較例1的表面處理劑,以下述方法,進行氮化矽基板(SiN)、矽熱氧化膜基板(Ox)及鎢基板(W)之表面處理。 具體而言,各基板於濃度0.5質量%的HF水溶液中於25℃浸漬1分鐘,進行前處理。上述前處理後,基板以離子交換蒸餾水洗淨1分鐘。將水洗後之基板藉由氮氣流乾燥。 乾燥後之各基板於上述各表面處理劑中於60℃浸漬10分鐘,進行基板之表面處理。表面處理後之基板以異丙醇中洗淨1分鐘後,以離子交換蒸餾水洗淨1分鐘。經洗淨後之基板藉由氮氣流乾燥,獲得經表面處理之基板。(Surface treatment) Using the surface treatment agents obtained in Examples 1 to 4 and Comparative Example 1, the surfaces of silicon nitride substrates (SiN), silicon thermal oxide film substrates (Ox) and tungsten substrates (W) were treated in the following manner. deal with. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, the substrates were immersed in the above-mentioned surface treatment agents at 60°C for 10 minutes to perform surface treatment of the substrates. The surface-treated substrate was washed with isopropanol for 1 minute, and then with ion-exchanged distilled water for 1 minute. The cleaned substrate was dried by nitrogen flow to obtain a surface-treated substrate.
(水的接觸角之測定) 針對上述HF前處理後之各基板、上述表面處理後之各基板測定水的接觸角。 水的接觸角之測定係使用Dropmaster700(協和界面科學股份公司製)於經表面處理之基板表面滴下純水液滴(2.0μL),測定滴下2秒後之接觸角。結果示於下述表1。又,表1中之接觸角差(°)係自前者之基板處理後的水接觸角減去後者基板之處理後的水接觸角之值後的值。(Measurement of Water Contact Angle) The water contact angle was measured for each of the substrates after the HF pretreatment and each of the substrates after the surface treatment. The measurement of the contact angle of water is to drop pure water droplets (2.0μL) on the surface of the surface-treated substrate using Dropmaster700 (manufactured by Kyowa Interface Science Co., Ltd.), and measure the contact angle after 2 seconds of dropping. The results are shown in Table 1 below. The contact angle difference (°) in Table 1 is the value obtained by subtracting the value of the water contact angle of the latter substrate after the treatment from the water contact angle of the former substrate after treatment.
如由上述表1所示之結果所了解,可知相較於不含化合物(B)之比較例1,使用與矽烷化劑(A)一起含有化合物(B)之實施例1、2之表面處理劑者,W基板與SiN或Ox基板之水接觸角差較大。 尤其可知使用與矽烷化劑(A)一起含有化合物(B)之實施例1、2的表面處理劑可較好地使用於利用ALD法之基板表面之區域選擇性製膜。As understood from the results shown in Table 1 above, it can be seen that the surface treatment of Examples 1 and 2 containing Compound (B) together with the silanizing agent (A) was compared to Comparative Example 1 not containing Compound (B). For those with different agents, the water contact angle difference between the W substrate and the SiN or Ox substrate is relatively large. In particular, it can be seen that the surface treatment agents of Examples 1 and 2, which contain compound (B) together with the silylation agent (A), can be preferably used for regioselective film formation on the surface of the substrate by the ALD method.
[實施例3~7] (表面處理劑之調製) 於溶劑乙酸3-甲基-3-甲氧基-1-丁酯中,均一混合下述表2中記載之各矽烷化劑(A) 7.8質量%、作為化合物(B)之咪唑1.0質量%,調製實施例3~7之表面處理劑。[Example 3~7] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, each silylating agent (A) recorded in the following Table 2 was uniformly mixed 7.8% by mass, 1.0% by mass of imidazole as the compound (B), prepared the surface treatment agents of Examples 3-7.
(表面處理) 使用所得之實施例3~7之表面處理劑,與實施例1、2及比較例1同樣,於以HF水溶液之前處理後,進行SiN基板、Ox基板、W基板及氮化鈦基板(TiN)之表面處理,針對上述HF前處理後之各基板、上述表面處理後之各基板,測定水的接觸角。 水的接觸角之測定與上述同樣進行。結果示於下述表2。又,表2中之接觸角差(°)係自前者之基板處理後的水接觸角減去後者基板之處理後的水接觸角之值後的值。(Surface treatment) Using the obtained surface treatment agents of Examples 3 to 7, as in Examples 1, 2 and Comparative Example 1, after pretreatment with HF aqueous solution, SiN substrate, Ox substrate, W substrate and titanium nitride substrate were performed. For the surface treatment of the substrate (TiN), the contact angle of water was measured for each substrate after the above-mentioned HF pretreatment and each substrate after the above-mentioned surface treatment. The measurement of the contact angle of water was carried out in the same manner as above. The results are shown in Table 2 below. In addition, the contact angle difference (°) in Table 2 is the value obtained by subtracting the value of the water contact angle of the latter substrate after the treatment from the water contact angle of the former substrate after treatment.
如由上述表2所示之結果所了解,可知以矽烷化劑之表面處理前(HF前處理後)之SiN基板、Ox基板、W基板及TiN基板於各基板間之水接觸角差較小。 另一方面,可知以含有各種矽烷化劑(A)及咪唑的實施例3~7之表面處理劑表面處理後,例如於表2之接觸角差欄所示之基板間,水接觸角差較大。 由該結果可說是使用含有各種矽烷化劑(A)及化合物(B)之表面處理劑之含複數不同區域之基板,可較好地適用於使用ALD法之基板表面之區域選擇性製膜。 尤其,使用直鏈狀烷基的碳原子數為8、11之實施例5、6的表面處理劑時,可知有W基板與SiN基板、Ox基板或TiN基板之水接觸角差特別大的傾向。As can be understood from the results shown in Table 2 above, it can be known that the SiN substrate, Ox substrate, W substrate, and TiN substrate before the surface treatment with the silanizing agent (after the HF pretreatment) have a small difference in water contact angle between the substrates. . On the other hand, it can be seen that after surface treatment with the surface treatment agents of Examples 3 to 7 containing various silylation agents (A) and imidazoles, for example, between the substrates shown in the contact angle difference column of Table 2, the water contact angle difference is relatively small. big. From this result, it can be said that the use of surface treatment agents containing various silanizing agents (A) and compounds (B) on substrates containing multiple different regions is better suitable for the region-selective film formation on the substrate surface using the ALD method. . In particular, when using the surface treatment agents of Examples 5 and 6 in which the linear alkyl group has 8 or 11 carbon atoms, it can be seen that the difference in water contact angle between the W substrate and the SiN substrate, Ox substrate, or TiN substrate tends to be particularly large. .
[實施例8] (表面處理劑之調製) 於下述各種溶劑中,均一混合作為矽烷化劑(A)之正辛基三甲氧基矽烷7.8質量%與作為化合物(B)之咪唑1.0質量%,調製表面處理劑。 異丙醇(IPA) 甲基乙基酮(MEK) 乙酸乙酯 3-甲基-3-甲氧基丁醇(MMB) 丙二醇單甲醚(PGME) 二乙二醇單甲醚(MDG) 丙二醇單甲醚乙酸酯(PGMEA) 乙酸3-甲基-3-甲氧基-1-丁酯(MMBA)[Example 8] (Preparation of surface treatment agent) In the following solvents, 7.8% by mass of n-octyltrimethoxysilane as a silylating agent (A) and 1.0% by mass of imidazole as a compound (B) were uniformly mixed , modulation surface treatment agent. Isopropyl alcohol (IPA) Methyl ethyl ketone (MEK) Ethyl acetate 3-methyl-3-methoxybutanol (MMB) Propylene glycol monomethyl ether (PGME) Diethylene glycol monomethyl ether (MDG) Propylene glycol Monomethyl ether acetate (PGMEA) 3-methyl-3-methoxy-1-butyl acetate (MMBA)
(表面處理) 使用所得之表面處理劑,與實施例1、2及比較例1同樣,於以HF水溶液之前處理後,進行Ox基板及W基板之表面處理,針對上述表面處理後之各基板,測定水的接觸角。 水的接觸角之測定與上述同樣進行。隨後,將Ox基板及W基板間之水接觸角差與各溶劑之介電率間的關係總結於圖1。(Surface treatment) Using the obtained surface treatment agent, the same as in Examples 1, 2 and Comparative Example 1, after pre-treatment with HF aqueous solution, carry out the surface treatment of the Ox substrate and the W substrate, for each substrate after the above-mentioned surface treatment, Measure the contact angle of water. The measurement of the contact angle of water was carried out in the same manner as above. Subsequently, the relationship between the water contact angle difference between the Ox substrate and the W substrate and the dielectric constant of each solvent is summarized in FIG. 1 .
基於圖1所示之Ox基板與W基板之間的水接觸角差及各種溶劑之介電率之關係,可知若為介電率1以上25以下之溶劑,則有該水接觸角差變大之傾向。 具體而言,基於材質不同之基板表面間之疏水性提高之選擇性之觀點,可知乙酸3-甲基-3-甲氧基-1-丁酯、乙酸乙酯或丙二醇單甲醚乙酸酯特佳。Based on the relationship between the water contact angle difference between the Ox substrate and the W substrate and the dielectric constants of various solvents shown in Figure 1, it can be known that the water contact angle difference becomes larger for solvents with a dielectric constant of 1 to 25 tendency. Specifically, from the viewpoint of the selectivity of hydrophobicity improvement between substrate surfaces of different materials, it can be known that 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate, or propylene glycol monomethyl ether acetate Excellent.
[實施例9及10以及比較例2及3] (表面處理劑之調製) 於溶劑乙酸3-甲基-3-甲氧基-1-丁酯中以5.0質量%均一混合六甲基二矽氮烷(HMDS),調製比較例2之表面處理劑。 除進一步混合作為化合物(B)之咪唑3.5質量%以外,與比較例2同樣調製實施例9之表面處理劑。 除代替HMDS 5.0質量%而均一混合正辛基三甲氧基矽烷5.0質量%以外,與比較例3同樣調製比較例3之表面處理劑。 除進一步混合作為化合物(B)之咪唑3.5質量%以外,與比較例3同樣調製實施例10之表面處理劑。[Examples 9 and 10 and Comparative Examples 2 and 3] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, 5.0% by mass of hexamethyldisilane was uniformly mixed Azane (HMDS) prepared the surface treatment agent of Comparative Example 2. The surface treatment agent of Example 9 was prepared in the same manner as in Comparative Example 2, except that 3.5% by mass of imidazole as compound (B) was further mixed. The surface treatment agent of Comparative Example 3 was prepared in the same manner as in Comparative Example 3, except that 5.0% by mass of n-octyltrimethoxysilane was uniformly mixed instead of 5.0% by mass of HMDS. The surface treatment agent of Example 10 was prepared in the same manner as in Comparative Example 3, except that 3.5% by mass of imidazole as compound (B) was further mixed.
(表面處理) 使用所得之實施例9及10及比較例2及3之表面處理劑,與實施例1、2及比較例1同樣,於以HF水溶液之前處理後,進行Si基板、SiN基板、Ox基板、W基板、鈷基板(Co)、氮化鈦基板(TiN)及氮化鉭基板(TaN)之表面處理,針對上述HF前處理後之各基板、上述表面處理後之各基板,測定水的接觸角。 水的接觸角之測定與上述同樣進行。結果示於下述表3及4。又,下表4及6中,顯示材質不同的基板間之水的接觸角之差值。又,表4及表6中之接觸角差(°)係自前者之基板處理後之水的接觸角減去後者之基板處理後之水的接觸角之值後之值。(Surface treatment) Using the surface treatment agents obtained in Examples 9 and 10 and Comparative Examples 2 and 3, as in Examples 1, 2 and Comparative Example 1, after pre-treatment with HF aqueous solution, Si substrates, SiN substrates, The surface treatment of Ox substrate, W substrate, cobalt substrate (Co), titanium nitride substrate (TiN) and tantalum nitride substrate (TaN) was measured for each substrate after the above HF pretreatment and each substrate after the above surface treatment. water contact angle. The measurement of the contact angle of water was carried out in the same manner as above. The results are shown in Tables 3 and 4 below. In addition, Tables 4 and 6 below show differences in contact angles of water between substrates of different materials. Also, the contact angle difference (°) in Table 4 and Table 6 is the value obtained by subtracting the contact angle of water after substrate treatment in the former from the contact angle of water after substrate treatment in the latter.
如由上述表3所示之結果所了解,可知相較於以不含咪唑之比較例2的表面處理劑表面處理時,以含咪唑之實施例9之表面處理劑表面處理之情況時,例如表4之接觸角差欄所示之基板間之水接觸角差較大。 使用與矽烷化劑(A)一起含有化合物(B)之實施例9之表面處理劑,可說是可較好地適用於使用ALD法之基板表面的區域選擇性製膜。As understood from the results shown in Table 3 above, it can be seen that when the surface is treated with the surface treatment agent of Example 9 containing imidazole, compared with the surface treatment with the surface treatment agent of Comparative Example 2 that does not contain imidazole, for example The water contact angle difference between the substrates shown in the contact angle difference column of Table 4 is relatively large. The use of the surface treatment agent of Example 9, which contains the compound (B) together with the silylation agent (A), can be said to be suitable for regioselective film formation on the substrate surface using the ALD method.
如由上述表5所示之結果所了解,可知相較於以不含咪唑之比較例3的表面處理劑表面處理時,以含咪唑之實施例10之表面處理劑表面處理之情況時,例如表6之接觸角差欄所示之基板間之水接觸角差較大。 使用與矽烷化劑(A)一起含有化合物(B)之實施例10之表面處理劑,可說是可較好地適用於使用ALD法之基板表面的區域選擇性製膜。As understood from the results shown in Table 5 above, it can be seen that when the surface is treated with the surface treatment agent of Example 10 containing imidazole, compared to the surface treatment with the surface treatment agent of Comparative Example 3 that does not contain imidazole, for example The water contact angle difference between the substrates shown in the contact angle difference column of Table 6 is relatively large. The use of the surface treatment agent of Example 10, which contains the compound (B) together with the silylation agent (A), can be said to be suitable for regioselective film formation on the surface of the substrate using the ALD method.
又,除了咪唑含量分別變更為0.5質量%、1質量%、3質量%以外,使用與實施例10之表面處理劑同樣的表面處理劑,對Si基板、SiN基板、Ox基板、W基板、Co基板、TiN基板及TaN基板進行表面處理之結果,獲得與表5及表6所示之結果相同的結果。In addition, except that the imidazole content was changed to 0.5% by mass, 1% by mass, and 3% by mass, the same surface treatment agent as in Example 10 was used to treat Si substrates, SiN substrates, Ox substrates, W substrates, and Co substrates. As a result of surface treatment of the substrate, TiN substrate, and TaN substrate, the same results as those shown in Table 5 and Table 6 were obtained.
[實施例11] (表面處理劑之調製) 於溶劑乙酸3-甲基-3-甲氧基-1-丁酯中以5.0質量%均一混合以往之矽烷化劑HMDS及咪唑3.5質量%,調製實施例4之表面處理劑。[Example 11] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, 5.0% by mass of the conventional silylation agent HMDS and 3.5% by mass of imidazole were uniformly mixed to prepare The surface treatment agent of embodiment 4.
(表面處理) 使用所得之實施例11之表面處理劑,以下述方法,進行Si基板、SiN基板、Ox基板及W基板之表面處理。 具體而言,各基板於濃度0.5質量%的HF水溶液中於25℃浸漬1分鐘,進行前處理。上述前處理後,基板以離子交換蒸餾水洗淨1分鐘。將水洗後之基板藉由氮氣流乾燥。 乾燥後之各基板於上述各表面處理劑中於25℃浸漬如下述表5所示之時間,進行基板之表面處理,針對各基板測定各浸漬時間之水接觸角。水接觸角之測定與上述同樣進行。結果示於下述表7。(Surface treatment) Using the surface treatment agent obtained in Example 11, the surface treatment of Si substrates, SiN substrates, Ox substrates and W substrates was carried out by the following method. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, each substrate was immersed in the above-mentioned surface treatment agents at 25°C for the time shown in Table 5 below to perform surface treatment of the substrate, and the water contact angle of each immersion time was measured for each substrate. The measurement of the water contact angle was carried out in the same manner as above. The results are shown in Table 7 below.
如由上述表7所示之結果所了解,可知無關於浸漬時間,W基板之水接觸角與Si、SiN或Ox基板之水接觸角的差較大。As understood from the results shown in Table 7 above, it can be seen that the water contact angle of the W substrate has a large difference from the water contact angle of the Si, SiN, or Ox substrate regardless of the immersion time.
[實施例12~14] (表面處理劑) 於溶劑乙酸3-甲基-3-甲氧基-1-丁酯91.5g中以5.0質量%均一混合HMDS與咪唑3.5質量%,調製實施例12之表面處理劑。 除了代替HMDS 5.0質量%而均一混合四甲基二矽氮烷(TMDS) 5.0質量%以外,與實施例12同樣調製實施例13之表面處理劑。 除了代替HMDS 5.0質量%而均一混合雙(二甲胺基)二甲基矽烷(BDMADMS) 5.0質量%以外,與實施例12同樣調製實施例14之表面處理劑。[Examples 12 to 14] (Surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate 91.5g, HMDS and imidazole 3.5 mass% were uniformly mixed at 5.0 mass%, and Example 12 was prepared. surface treatment agent. The surface treatment agent of Example 13 was prepared in the same manner as in Example 12, except that 5.0% by mass of tetramethyldisilazane (TMDS) was uniformly mixed instead of 5.0% by mass of HMDS. The surface treatment agent of Example 14 was prepared in the same manner as in Example 12, except that 5.0% by mass of bis(dimethylamino)dimethylsilane (BDMADMS) was uniformly mixed instead of 5.0% by mass of HMDS.
(表面處理) 使用所得之實施例12~14之表面處理劑,以下述方法,進行SiN基板、Ox基板、Co基板及TiN基板之表面處理。 具體而言,各基板於濃度0.5質量%的HF水溶液中於25℃浸漬1分鐘,進行前處理。上述前處理後,基板以離子交換蒸餾水洗淨1分鐘。將水洗後之基板藉由氮氣流乾燥。 乾燥後之各基板於上述各表面處理劑中於60℃浸漬10分鐘,進行基板之表面處理。經表面處理後之基板以異丙醇洗淨1分鐘後,以離子交換蒸餾水進行1分鐘洗淨。經洗淨之基板藉由氮氣流乾燥,獲得經表面處理之基板。水接觸角之測定與上述同樣進行。結果示於下述表8。(Surface Treatment) Using the obtained surface treatment agents of Examples 12 to 14, the surface treatment of SiN substrates, Ox substrates, Co substrates and TiN substrates was carried out by the following method. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, the substrates were immersed in the above-mentioned surface treatment agents at 60°C for 10 minutes to perform surface treatment of the substrates. The surface-treated substrate was washed with isopropanol for 1 minute, and then washed with ion-exchanged distilled water for 1 minute. The cleaned substrate was dried by nitrogen flow to obtain a surface-treated substrate. The measurement of the water contact angle was carried out in the same manner as above. The results are shown in Table 8 below.
如由上述表8所示之結果所了解可知,以含有各種矽烷化劑(A)及咪唑之實施例12~14之表面處理劑表面處理後,與SiN或Ox基板之水接觸角差較大。另一方面,由於與Co或TiN基板之水接觸角差減小,故可知實施例12~14具有選擇性。As can be understood from the results shown in Table 8 above, after surface treatment with the surface treatment agents of Examples 12 to 14 containing various silanizing agents (A) and imidazoles, the difference in water contact angle with SiN or Ox substrates is relatively large . On the other hand, since the difference of the water contact angle with the Co or TiN substrate is reduced, it can be seen that Examples 12 to 14 have selectivity.
(耐熱性評價) 使用所得之實施例12~實施例14之表面處理劑,以下述方法,進行SiN基板及Ox基板上之耐熱性評價。 具體而言,於上述各表面處理劑中以時間1分鐘及溫度25℃予以浸漬,進行SiN基板與Ox基板之表面處理。隨後,於氮氣環境下,以加熱板於300℃烘烤,針對各基板測定經過各烘烤時間時之水接觸角。結果示於表9。(Evaluation of heat resistance) Using the surface treatment agents obtained in Examples 12 to 14, the heat resistance evaluations on SiN substrates and Ox substrates were performed by the following method. Specifically, immerse in each of the above-mentioned surface treatment agents for 1 minute at a temperature of 25°C to perform surface treatment of the SiN substrate and the Ox substrate. Subsequently, under a nitrogen atmosphere, a heating plate was used to bake at 300° C., and the water contact angle was measured for each substrate after each baking time. The results are shown in Table 9.
如由上述表9所示之結果所了解,使用TMDS或BDMADMS時,即使加熱時亦可以高水準維持水接觸。由此認為,使用該等矽烷化劑之情況,即使將經表面處理之基板交付於原子層成長法等之高溫製程時,亦可穩定地保持矽烷化部位,而期待亦可較好地使用於工業製程。As is clear from the results shown in Table 9 above, when TMDS or BDMADMS is used, water contact can be maintained at a high level even when heated. From this, it is considered that the use of these silanizing agents can stably maintain the silanized sites even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth method, and it is expected to be better used in industrial process.
圖1係顯示Ox基板及W基板間之水接觸角差與各種溶劑之介電率之關係的圖。FIG. 1 is a graph showing the relationship between the water contact angle difference between an Ox substrate and a W substrate and the dielectric constant of various solvents.
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