201124487 六、發明說明： 【發明所屬之技術領域】 本發明係關於為了形成多孔質膜而利用旋塗法塗佈之多 孔質膜的前驅物組成物，尤其侧於由有機魏化物所構成 之多孔質膜的前驅物組成物及使用該前驅物組成物的多孔質 膜之成膜方法。 【先前技術】 近年來，隨著搭載半導體裝置之機器的縮小化之進行，對 於構成半導體裝置之元件或佈線之細微化與緻密化的要求曰 漸心：南。由於元件及佈線之細微化進行會使佈線延遲明顯化， 因此亦要求佈線間之低容量化，俾抑制因佈線延遲所造成的處 理速度之降低。目而’於f知技射，為了尋求該佈線間之低 容量化’係例如專利文獻1所記載般，深入研究以多孔質之有 機矽氧化物膜(亦即多孔質二氧化矽膜)構成佈線間之絕緣膜。 在利用旋塗法形成上述多孔質二氧化矽膜之方法中，首先 係於基板上塗佈多孔質膜之前驅物組成物。接著，經由基板之 加熱，將前驅物組成物中所含之熱分解性有機化合物分解，形 成熱分解性有機化合物所佔有之空間成為空孔之狀態的有機 矽氧化物膜，亦即多孔質二氧化矽膜。之後，對於多孔質二氧 化矽膜之表面整體，導入疏水性之官能基。疏水性之官能基亦 被導入露出於多孔質二氧化矽膜表面的空孔之内表面。根據如 此形成之多孔質二氧化矽膜，可抑制親水性化合物進入空孔 内，因此可抑制親水性化合物所造成之介電係數的上升，而可 4 201124487 維持多孔質二氧化矽膜原本所具有之低介電常數。 [專利文獻] r (專利文獻1)曰本專利特開2006-265350號公報 【發明内容】 (發明所欲解決之問題） 然而’若使用上述多孔質二氧化賴作為佈線間之絕緣 膜，則用以形成佈線或電極等之溝或貫通孔會被形成在該多孔 質二氧化賴。然後’由於_般係使用乾式侧處理作為形成 細微的溝或貫通孔之方法，故對於上述纽f二氧化賴係施 行乾式蝕刻處理。 另一方面，在實施乾式蝕刻處理之反應容器内的氣相中， 用於侧之氣體之賴被引發，生成作為侧劑之正離子或自 由基。然後，含有正離子或自由基之_劑將上述多孔質二氧 化石夕膜予以物雖或化學性侧，藉此軸上料或貫通孔。 此時’最初係石夕與氧之鍵結因银刻劑而被切斷，而導入至空孔 内表面之上述疏水性官能基财_結亦被侧咖斷。其結 果’在多孔質二氧化石夕膜中，疏水性官能基脫離之部位會吸 附親水性化合物，例如大氣中之水分子。 亦P在上述專利文獻1所記載之從前驅物組成物形成多 孔質二氧化頻的情況’於該形成時，多孔f二氧切膜之低 介電係數化雖魏，健過使贼式_處理之加I後，會有 多孔質二氧化矽膜失去低介電係數特性之虞。 本發明係有鏗於上述習知實情而完成者，其目的在於提供 201124487 一種可抑制多孔質膜的介電常數在其蝕刻加工後增加之多孔 質膜之前驅物組成物，以及使用其之多孔質膜的成膜方法。 (解決問題之手段） 本發明之第一態樣係提供一種多孔質膜之前驅物組成 物，其含有：第一烷氧基矽烷化合物、第二烷氧基矽烷化合物、 以及在上述第一烷氧基矽烷化合物與上述第二烷氧基矽烷化 合物發生共聚合之溫度以上會破壞之非離子性界面活性劑微 胞。上述第一烧氧基石夕烧化合物係從由四烧氧基石夕烧、二烧基 二烷氧基矽烷、四烷氧基矽烷之聚合體、以及二烷基二烷氧基 矽烷之聚合體所組成群組中選擇之至少一者，上述第二烷氧基 矽烷化合物係於直鏈飽和烴之兩末端具有三烷氧基矽烷基之 烧氧基石夕烧化合物。 根據上述構成，在第一烷氧基石夕烷化合物與第二烷氧基矽 烷化合物發生共聚合之條件下，會形成以聚矽氧烷骨架作為主 骨架之有機矽氧化膜，而該有機矽氧化膜中係含有非離子性界 面活性劑微胞。然後，在第一烷氧基矽烷化合物與第二烷氧基 矽烷化合物發生共聚合之溫度以上，有機矽氧化膜中所含之非 離子性界面活性劑微胞被破壞，在該微胞佔有之空間形成空 孔。因此，以聚矽氧烷骨架作為主骨架之多孔質膜的空孔率(亦 即介電係數)係由非離子性界面活性劑微胞之含有量所決定。 此時，於直鏈飽和烴之兩末端具有三烷氧基矽烷基之烷氧 基石夕烷化合物係第二烷氧基矽烷化合物，故於構成多孔質膜之 單位骨架内，係含有該第二烷氧基矽烷化合物所具有之直鏈型 德和煙。藉此’在對多孔質膜應用乾式蝕刻處理之情況，即便 201124487 上述直鏈飽和烴之任—者與鄰接於其之原子的鍵結被切斷，仍 可抑制烴基之脫離。又，由於如此抑制烴之脫離，該烴與鄰接 於其之原子之鍵結亦容易修復。因此，可抑制起因於烴之脫離 的水分子之吸附，因而可抑制多孔質膜之蝕刻加工後的介電常 數之增大。 若烧氧基>5夕烧化合物所具有之烷氧基或烷基的碳數變 多，則在烷氧基矽烷化合物之聚合時，一般而言烷氧基矽烷化 合物間之分子間距離變長。因此’在多孔質膜之聚合度低，在 去除了上述空孔之部分，難以促進膜之緻密化。在如上述之多 孔質膜之情況下，由於多孔質膜之空孔率(亦即多孔質膜之介 電係數)係由非離子性界面活性劑微胞之含有量所擔保，故對 於去除了空孔之部分，不需要進一步之空孔。當然，若從確保 多孔質膜之機械強度或保護膜中之疏水基的觀點而言，可促進 膜之緻密化的構成為較佳。 因此’在一例中，第一烷氧基矽烷化合物係從由四曱氧基 石夕燒、四乙氧基矽烷、屬於四曱氧基矽烷之聚合體的甲基矽酸 鹽、二甲基二曱氧基矽烷、以及二曱基二乙氧基矽烷所組成群 組中選擇之至少一者。此情況，由於第一烷氧基矽烷化合物係 具有碳數為1或2之烷氧基的烷氧基矽烷化合物，在去除了空 孔之部分可促進膜之緻密化，因此可確保多孔質膜之機械強 度’或更確實地保護膜中之疏水基。 若如上述般，烷氧基矽烷化合物所具有之烷氧基的碳數變 夕’則於烧氧基石夕烧化合物之聚合時，一般而言烧氧基石夕烧化 合物間之分子間距離變長，在上述去除了空孔之部分，難以促 201124487 進膜之緻密化。從確保多孔質膜之機械強度或保護膜中之疏水 基的觀點而言，可促進膜之緻密化的構成為較佳。因此，在一 例中’第二燒氧基矽烷化合物之各烷氧基係碳原子數1〜3之烷 氧基。因此，在去除了空孔之部分，可促進膜之緻密化，故可 確保多孔質膜之機械強度，或更確實地保護膜中之疏水基。 為了抑制多孔質膜所具有之介電係數的上升，使環境中所 存在之水與多孔質膜不具有親和性，亦即提高該多孔質膜之疏 水性，係有效果的。由於上述第二烷氧基矽烧化合物所具有之 飽和烴骨架係為疏水性，故藉由將其導入多孔質膜中，可對該 多孔質驊賦予疏水性。又，如此所導入於多孔質膜之飽和烴骨 架之數量越多，則該多孔質膜之疏水性程度亦增加。 另一方面，以經驗上而言，亦已知隨著對多孔質膜導入之 飽和烴骨架數量之增加，其機械強度會降低。此現象可認為係 因對作為多孔質膜骨架之例如聚矽氧烷大量導入烴基，聚矽氧 烷骨架之每單位的大小變大，亦即骨架成為更為疏離之狀態。 亦即，在多孔質膜所具有之疏水性與機械強度之間，係成立所 謂互償(trade-off)之關係。 因此，在一例中，第二烷氧基矽烷化合物之物質量，係被 調整為使多孔質膜的疏水性提升且不使該多孔質膜之機械強 度降低的範圍，亦即大於第一烷氧基矽烷化合物中所含之矽原 子數的5at%且未滿50at°/。之範圍。藉此，可兼顧確保由第二烷 氧基石夕烧化合物對多孔質膜所賦予之疏水性，以及抑制該多孔 質膜之機械強度的降低。 本發明之另一態樣提供多孔質臈之成膜方法.，其包含··將 8 201124487 含有第一烷氧基矽烷化合物、第二烷氧基矽烷化合物、以及在 上述第一烷氧基矽烷化合物與上述第二烷氧基矽烷化合物發 生共聚合之溫度以上會破壞之非離子性界面活性劑微胞的多 孔質膜之前驅物組成物，利用旋塗法而塗佈於基板之步驟；將 塗佈有上述多孔質膜之前驅物組成物的基板，升溫至上述第一 烧氧基梦烧化合物與上述第二院氧基矽烧化合物發生共聚合 之溫度為止之步驟；以及將經破壞之上述非離子性界面活性劑 微胞’從上述第一烷氧基矽烷化合物與上述第二烷氧基矽烷化 合物之共聚合體中去除之步驟。上述第一烷氧基矽烷化合物係 從由四烷氧基矽烷、二烷基二烷氧基矽烷、四烷氧基矽烷之聚 合體、以及二烷基二烷氧基矽烷之聚合體所組成群組中選擇之 至少一者’上述第二烷氧基矽烷化合物係於直鏈飽和烴之兩末 端具有三烷氧基梦烷基之烷氧基矽烷化合物。 根據該方法，可獲得與上述第一態樣相同的作用效果。本 發明.之其他態樣及優點經由下述說明則可更為明瞭。 【實施方式】 &以下，針對將本發明之多孔質膜之前驅物組成物以及使用 該前驅物組成物之多孔質膜的成膜方法予以具體化之一實施 形態，進行說明。 本實施形態之使用前驅物組成物所形成的多孔質膜，係多 孔質之有機魏氧化物膜，亦即多孔質二氧化麵，該多孔質 二氧化頻之構造單_町雜學式⑴絲*(下標字a、 b、c及X係整數）。此種多孔質二氧化石夕膜係由含有⑻第一烷 201124487 氧基石夕烧化合物、(b)l分子内具有2個石夕原子之第二烧氧基石夕 烧化合物、_離子性界面活_微胞之前驅物組成物所形 (化1)[Technical Field] The present invention relates to a precursor composition of a porous film coated by a spin coating method for forming a porous film, in particular, a porous body composed of an organic derivative. A precursor composition of a plasma membrane and a method of forming a porous film using the precursor composition. [Prior Art] In recent years, as the reduction of the device in which the semiconductor device is mounted has progressed, the requirements for the miniaturization and densification of the components or wirings constituting the semiconductor device have been gradually increased. Since the wiring delay is made clear by the miniaturization of the components and the wiring, the capacity between the wirings is required to be reduced, and the processing speed due to the wiring delay is suppressed. In order to find a low capacity between the wirings, for example, as described in Patent Document 1, a porous organic cerium oxide film (that is, a porous cerium oxide film) is intensively studied. Insulating film between wirings. In the method of forming the porous ceria film by a spin coating method, first, a porous film precursor composition is applied onto a substrate. Then, the thermally decomposable organic compound contained in the precursor composition is decomposed by heating of the substrate to form an organic tantalum oxide film in a state in which the space occupied by the thermally decomposable organic compound is in the form of pores, that is, porous Oxide film. Thereafter, a hydrophobic functional group is introduced to the entire surface of the porous ruthenium dioxide film. The hydrophobic functional group is also introduced into the inner surface of the pore exposed on the surface of the porous ceria film. According to the porous ceria film thus formed, the hydrophilic compound can be prevented from entering the pores, so that the increase in the dielectric constant caused by the hydrophilic compound can be suppressed, and the porous ceria film can be maintained at 4 201124487. Low dielectric constant. [Patent Document 1] [Patent Document 1] JP-A-2006-265350 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, if the above porous dioxide is used as an insulating film between wirings, A groove or a through hole for forming a wiring or an electrode or the like is formed in the porous dioxide. Then, since the dry side treatment is used as a method of forming fine grooves or through holes, the dry etching treatment is performed on the above-mentioned neon oxide. On the other hand, in the gas phase in the reaction vessel subjected to the dry etching treatment, the gas for the side is induced to generate a positive ion or a radical as a side agent. Then, the porous cerium oxide or the radical-containing agent is applied to the porous oxidized oxide film or chemically on the side, thereby axially feeding or through-hole. At this time, the bond between the first stone and the oxygen was cut by the silver smear, and the hydrophobic functional group introduced into the inner surface of the pore was also broken. As a result, in the porous silica dioxide film, a portion where the hydrophobic functional group is detached adsorbs a hydrophilic compound such as water molecules in the atmosphere. Also, in the case of forming a porous dioxygenation frequency from the precursor composition described in the above Patent Document 1, the low dielectric constant of the porous f-dioxylyzed film is formed by the Wei, and the thief is _ After the addition of I, the porous cerium oxide film loses its low dielectric constant characteristics. The present invention has been completed in view of the above-described conventional circumstances, and an object thereof is to provide a porous film precursor composition capable of suppressing a dielectric constant of a porous film from being etched after the etching process, and a porous body using the same. Film formation method of plasma membrane. (Means for Solving the Problem) The first aspect of the present invention provides a porous film precursor composition comprising: a first alkoxydecane compound, a second alkoxydecane compound, and the first alkane described above The nonionic surfactant micelle which is destroyed at a temperature at which the oxydecane compound and the second alkoxydecane compound are copolymerized. The first alkoxylated compound is obtained from a polymer of tetra-oxo-oxygen, a dialkyl dialkoxy decane, a tetraalkoxy decane, and a polymer of a dialkyl dialkoxy decane. At least one selected from the group consisting of the second alkoxydecane compound is an alkoxylated compound having a trialkoxyalkyl group at both ends of a linear saturated hydrocarbon. According to the above configuration, under the condition that the first alkoxy oxalate compound and the second alkoxy decane compound are copolymerized, an organic ruthenium oxide film having a polysiloxane skeleton as a main skeleton is formed, and the organic ruthenium oxide is oxidized. The membrane contains nonionic surfactant micelles. Then, at a temperature at which the first alkoxydecane compound and the second alkoxydecane compound are copolymerized, the nonionic surfactant microcapsules contained in the organic tantalum oxide film are destroyed, and the microcapsules are occupied. The space forms a hole. Therefore, the porosity (i.e., the dielectric constant) of the porous film having the polysiloxane skeleton as the main skeleton is determined by the content of the nonionic surfactant microcapsules. In this case, the alkoxy oxalin compound having a trialkoxyalkylalkyl group at both ends of the linear saturated hydrocarbon is a second alkoxy decane compound, and thus the second skeleton is included in the unit skeleton constituting the porous membrane. The linear alkane and smoke of the alkoxydecane compound. Therefore, in the case where the dry etching treatment is applied to the porous film, even if the bond of any of the above-mentioned linear saturated hydrocarbons and the atom adjacent thereto is cut off in 201124487, the detachment of the hydrocarbon group can be suppressed. Further, since the detachment of the hydrocarbon is suppressed as described above, the bonding of the hydrocarbon to the atom adjacent thereto is also easily repaired. Therefore, the adsorption of water molecules due to the detachment of hydrocarbons can be suppressed, so that the increase in the dielectric constant after the etching of the porous film can be suppressed. When the alkoxy group or the alkyl group of the alkoxy group is increased, the molecular distance between the alkoxydecane compounds is generally changed in the polymerization of the alkoxydecane compound. long. Therefore, the degree of polymerization in the porous film is low, and it is difficult to promote densification of the film in the portion where the pores are removed. In the case of the porous film as described above, since the porosity of the porous film (that is, the dielectric constant of the porous film) is secured by the content of the nonionic surfactant microcapsule, it is removed. The part of the hole does not require further holes. Of course, it is preferable to promote the densification of the film from the viewpoint of securing the mechanical strength of the porous film or the hydrophobic group in the protective film. Therefore, 'in one example, the first alkoxydecane compound is a methyl phthalate from a polymer of tetramethoxy oxime, tetraethoxy decane, tetramethoxy decane, dimethyl hydrazine. At least one selected from the group consisting of oxoxane and dimercaptodiethoxydecane. In this case, since the first alkoxydecane compound is an alkoxydecane compound having an alkoxy group having 1 or 2 carbon atoms, the densification of the film can be promoted in the portion where the pores are removed, thereby ensuring the porous film. The mechanical strength 'or more reliably protects the hydrophobic groups in the film. As described above, when the carbon number of the alkoxy group of the alkoxydecane compound changes, the intermolecular distance between the alkoxylated compounds is generally longer when the alkoxylated compound is polymerized. In the above-mentioned part where the void is removed, it is difficult to promote the densification of the film into 201124487. From the viewpoint of securing the mechanical strength of the porous film or the hydrophobic group in the protective film, a structure which can promote densification of the film is preferable. Therefore, in one example, each alkoxy group of the 'second alkoxydecane compound is an alkoxy group having 1 to 3 carbon atoms. Therefore, the densification of the film can be promoted in the portion where the void is removed, so that the mechanical strength of the porous film can be ensured, or the hydrophobic group in the film can be more surely protected. In order to suppress an increase in the dielectric constant of the porous film, it is effective to prevent the water present in the environment from having an affinity with the porous film, that is, to improve the water repellency of the porous film. Since the saturated hydrocarbon skeleton of the second alkoxy sinter compound is hydrophobic, it can be imparted with hydrophobicity to the porous ruthenium by introducing it into the porous membrane. Further, as the number of saturated hydrocarbon skeletons introduced into the porous membrane as described above increases, the degree of hydrophobicity of the porous membrane also increases. On the other hand, empirically, it is also known that as the number of saturated hydrocarbon skeletons introduced into the porous membrane increases, the mechanical strength thereof decreases. This phenomenon is considered to be because a large amount of a hydrocarbon group is introduced into a porous membrane skeleton, for example, a polysulfide skeleton, and the size per unit of the polyoxane skeleton becomes large, that is, the skeleton becomes more sparse. That is, between the hydrophobicity and the mechanical strength of the porous film, a so-called trade-off relationship is established. Therefore, in one example, the mass of the second alkoxydecane compound is adjusted so as to increase the hydrophobicity of the porous film and not to lower the mechanical strength of the porous film, that is, to be larger than the first alkoxylate. 5 at% of the number of germanium atoms contained in the decane compound and less than 50 at °/. The scope. Thereby, both the hydrophobicity imparted to the porous film by the second alkoxylated compound can be ensured, and the decrease in the mechanical strength of the porous film can be suppressed. Another aspect of the present invention provides a film forming method for porous tantalum, comprising: 8 201124487 comprising a first alkoxydecane compound, a second alkoxydecane compound, and the first alkoxydecane described above a step of applying a porous film precursor composition of a nonionic surfactant microparticle which is destroyed by a compound to a temperature at which the compound is copolymerized with the second alkoxydecane compound, and is applied to the substrate by a spin coating method; a step of heating the substrate coated with the porous film precursor composition to a temperature at which the first oxy-oxyl compound and the second oxy-sinter compound are copolymerized; and destroying The step of removing the nonionic surfactant microcell 'from the copolymer of the first alkoxydecane compound and the second alkoxydecane compound described above. The first alkoxydecane compound is a group consisting of a polymer of a tetraalkoxy decane, a dialkyl dialkoxy decane, a tetraalkoxy decane, and a polymer of a dialkyl dialkoxy decane. At least one selected from the group 'the second alkoxydecane compound is an alkoxydecane compound having a trialkoxymonyl group at both ends of a linear saturated hydrocarbon. According to this method, the same effects as those of the first aspect described above can be obtained. Other aspects and advantages of the invention will become apparent from the following description. [Embodiment] The film formation method of the porous film precursor composition of the present invention and the porous film using the precursor composition will be described below. The porous film formed using the precursor composition of the present embodiment is a porous organic Wei oxide film, that is, a porous dioxide surface, and the porous dioxygenated structure is a single-method (1) wire. * (subscript a, b, c, and X are integers). The porous silica dioxide film is composed of (8) a first alkane 201124487 oxy-stone compound, (b) a second alkoxy sulphide compound having two austenite atoms in the molecule, and an ionic interface _ Microcell precursor composition (form 1)
R-[〇-Si]a-[〇-Si-(cH2)x -Si^^o-siR^-OR (a)第一烷氧基矽烷化合物 作為第-錄基⑦舰合物，係含樣由四烧氧基石夕烧、 ，二烧基二錄基魏、四絲基魏之聚合體、以及二烧基二 烧氧基石夕烧之聚合體所構成之群組選擇的至少—者。作為院氧 基’較佳係採用曱氧基、6氧基以及丙氧基，該等之組合亦為 任意。作為烷基，較佳係採用甲基、乙基以及丙基，該等之組 合亦為任意。此種第一烷氧基矽烷化合物係可舉例如四甲氧基 矽烷、四乙氧基矽烷、甲基矽酸鹽、二曱基二甲氧基矽烷以及 一甲基二乙氧基矽烷。另外，上述曱基矽酸鹽係為四曱氧基矽 烷之多聚物，例如四甲氧基矽烷之四聚物(參照化學式(2))。 (化2)R-[〇-Si]a-[〇-Si-(cH2)x -Si^^o-siR^-OR (a) a first alkoxydecane compound as a first-record 7 saponin, The sample is selected from the group consisting of a group of four kinds of alkaloids, a group of dicalcyl sulphide, a group of tetrasyl ketones, and a polymer of a dialkyl oxyalkylene group. The oxy group, the oxy group, the oxy group and the propyloxy group are preferably used as the hospital oxygen group, and the combinations thereof are also arbitrary. As the alkyl group, a methyl group, an ethyl group and a propyl group are preferably used, and the combinations thereof are also arbitrary. The first alkoxydecane compound may, for example, be tetramethoxy decane, tetraethoxy decane, methyl decanoate, dimercapto dimethoxy decane or monomethyldiethoxy decane. Further, the above mercapto citrate is a polymer of tetradecyloxydecane, for example, a tetramer of tetramethoxynonane (see Chemical Formula (2)). (chemical 2)
Sl’4〇3(〇CH3)10 ⑵ 第一烧氧基石夕烧化合物係藉由發生構成其之單體或聚合 體之2個以上分子間之脫醇縮聚合反應，形成上述化學式(1) 所示之一部分之聚矽氧烷骨架(參照下述化學式(3))。 (化3) R - [0-Si]a - or …⑶ (b)第二烷氧基矽烷化合物 第一烧氧基碎烧化合物係於直鏈飽和烴骨架之兩末端具 201124487 有三烷氧基矽烷基者，係由下述化學式(4)而一般化。 (化4) (R〇) 3 S i - (CH2)x -s i (0R)3 …（4) 構成化學式⑷中之下標x(亦即直鏈飽和烴骨架)之碳原子 數較佳為1〜3。三烷氧基矽烷基之各烷氧基的碳原子數較佳為 1〜3 °若為該等之範圍，則直鏈飽和烴骨架與烷氧基之組合亦 為任意。又’第二烷氧基矽烷化合物可單獨使用，亦可併用2 種類以上。作為此種第二烷氧基矽烷化合物，係例如為雙(三 甲氧基矽烷)甲烷、雙(三乙氧基矽烧)甲烷、雙(三丙氧基矽烷） 甲烷、雙(三甲氧基石夕烧)乙烷、雙(三乙氧基矽燒)乙烷、雙(三 丙氧基矽烷)乙烷、雙(三？氧基矽烷)丙烧、雙(三乙氧基石夕烧） 丙烷、雙(三丙氧基矽烷)丙烷等。 第一烷氧基矽烷化合物係藉由發生二個以上之分子間脫 醇聚縮合反應，而形成上述化學式⑴之—部分所示之骨架， ，P以直鏈飽和烴之兩末端被列子所包夾之構成作為構造 單位的骨轉訂述辨式⑼。糾，於第—缝基魏化 合物與第二錄基魏化合物之間，藉由發生二個社之分子 =醇騎合反應，㈣成社述化學式⑴作為構 骨架。 (化5) R-[〇_Si-(CH2)x-Si]b, ...⑸ (c)非離子性界面活性劑微胞 11 201124487 伸乙基驗、脂肪酸聚氧化伸乙基醋、脂肪酸聚氧化伸乙基山梨 醇_旨、聚丙二醇聚氧化伸乙基加成物等。又，亦可使用一般 稱為多7〇醇型之脂贿山轉㈣、麟、脂肪酸聚 甘油酯等。 此種非離子性界面活性舰於溶解有⑻第_^氧基石夕烧 化合物或(b)第二烧氧基魏化合物等之非水系溶媒中，利用 該界面活性劑之分子間的疏水性相互制*會合，形成屬於球 狀構造體之織。會合之雜子性界賴奸的疏水基末 端係朝向微胞之巾^，財合之雜子性界面活_分子的親 水基形成該微胞之外表面。.另外，非離子性界面活性劑微胞係 具有在第一烷氧基矽烷化合物或第二烷氧基矽烷化合物發生 共聚合之溫度以上，會被構造性破壞之溫度特性。 然後’若微胞形成於溶解有第一烧氧基石夕烧化合物或第二 烷氧基矽烷化合物等之非水系溶媒中，藉由與其之靜電相互作 用’第一烧氧基矽烧化合物或第二烧氧基矽烧化合物會集合於 該微胞之周圍。如此，若在第一烷氧基矽烷化合物或第二烷氧 基矽烷化合物集合於該微胞周圍之狀態下，進行上述之聚縮合 反應，則第一烷氧基矽烷化合物與第二烷氧基矽烷化合物之共 聚合體係以包圍微胞之方式形成。然後，由第一烷氧基矽烷化 合物與第二烷氧基矽烷化合物之共聚合體去除微胞，則於微胞 存在之區域形成空孔。如此所形成之空孔的直徑係與非離子性 界面活性劑之分子量成比例，因此當欲使空孔孔徑較大之情 況’選擇較大分子量之界面活性劑即可，另一方面，欲使空孔 徑較小之情況，則選擇較小分子量之界面活性劑即可。如此， 12 201124487 非離子性界面·_發揮作輕孔之频的功用。 ⑷非水系溶媒 ' ° 上述前驅物域物中，除了上述第—燒氧基魏化合物、 第-烧氧基魏化合物以及非料性界綠性舰胞之外，係 使用用以溶解該等之非水系溶媒。作轉水性溶媒係為醇 系、丙酉同系、韃系以及酉旨系，該等係於進行上述聚合反應之前 或者進行反麟從前驅物組成物巾去除，較健其彿點大於 75 C且未滿13()。(：之溶媒。作為此種非水系溶媒，例如可使用 屬於醇系之乙醇(彿點：78.4。〇、屬於_系之甲基乙基嗣(彿 點·: 79.6。。〇、甲基異丁基酮(沸點：116吻與甲基正頂沸 點：127°C)、屬於_之κ二氧陸園(沸點：仙此卜以及 屬於酯系之醋酸異丁S旨(彿點：118。〇與醋酸正丙醋(沸點： ].〇2°C)、醋酸正丁醋(彿點：125]26ΐ：)。 (e)反應觸媒 上述前驅物組成物中，除了該等各種化合物之外，可使用 促進上述第-烧氧基魏化合物與第^烧氧基魏化合物的 4縮合反應之觸媒、或肋調整聚合開始溫度之觸媒，作為反 應觸媒。作為反應麟’可使用酸觸，其例可舉出稀确酸。 另外，為了將添加稀猶所引起之前驅物組成物_性化予以 中和’並調整其pH，亦可添加氫氧化三甲基铵等之驗。 若為上述構成所形成之前驅物組成物，將前驅物組成物加 熱至非水系溶媒的沸點附近，則會促進前驅物組成物中所含之 非水系溶媒的蒸發，第一烷氧基矽烷化合物與第二烷氧基矽烷 化合物集合至非離子性界面活性劑微胞之周圍。若進一步將前 13 201124487 驅物組成物加熱至第一烷氧基矽烷化合物與第二烷氧基矽烷 化合物開始共聚合之溫度，則會形成以聚矽氧烷骨架作為主骨 架之有機矽氧化膜，於該有機矽氧化膜中係含有非離子性界面 活性劑微胞。然後，若將上述前驅物组成物加熱至第一烷氧基 矽烷化合物與第二烷氧基矽烷化合物共聚合之溫度以上，則有 機石夕氧化膜所含之非離子性界面活性劑微胞被破壞，於該微胞 所佔有之空間形成空孔。因此，以聚矽氧烧骨架作為主骨架之 多孔質二氧化矽膜的空孔率(亦即介電常數)亦由非離子性界 面活性劑微胞之含有量而決定。 此時，由於係使用具有直鏈飽和烴骨架之有機二矽化合物 作為第二烷氧基矽烷化合物，故除了多孔質二氧化矽膜之表層 當然含有飽和烴魏之外，；|於三駐骨架之聚魏烧骨架中 亦含有飽和烴骨架。脚，以含有於構成多孔質二氧化頻之 聚石夕氧烧縣巾的形式，對纽質二氧化賴帽予飽和烴骨 架。另外，纽質二氧切膜整齡賦予疏水性高的飽和烴骨 架。其結果’ g卩便在對纽質二氧化视_乾式侧處理之 情況，相較於飽和烴基與奴間的鍵結随刻而被切斷之情 兄飽和4月架與石夕之鍵結不易因姓刻而被切斷。因此，可抑 制多孔質二氧化賴中疏水性之降低，可抑制多孔質二氧化石夕 膜之介電係數在其加工後増加。 刊π炒犋所具有之烷氧基或烷基的碳原 加，則烧氧基石夕燒化合物間之分子間距離一般而言係變 長二在去除了上述空孔之部分，難以促進膜之緻密化。於上述 之多孔質二氧化频之情況，由於多孔質二氧靖之空孔ί 201124487 (亦多孔質二氧化矽膜之介電係數)係由非界面活性劑微胞 之含有量所確保，因此對於去除了空孔之部分，不需要進一步 的空孔。而從確保多孔質二氧化矽膜之硬度或保護膜中之疏水 f的觀點而言，較佳係促賴之緻密化的構成。由此觀點而 »作為第一燒氧基矽烧化合物，較佳為四甲氧基矽烧、四乙 氧基矽烷、屬於四曱氧基矽烷之聚合體的甲基矽酸鹽、二甲基 二甲氧基矽烷、以及二甲基二乙氧基矽烷。又，第二烷氧基矽 烷，合物中之烷氧基，亦以碳原子數K3之烷氧基為佳。根據 該等之構成，在去除了空孔之部分，可促賴之_化，因此 τ碟保多孔質二氧化⑦膜之機械強度或更卻實地保護膜中之 疏水基。 又，前驅物組成物中第一烷氧基矽烷化合物之Si原子組 成比百分率，從屬於主雜之聚魏财架賴狀的長度或三 T之展開大如且以作為多孔質二氧化補之機械硬度指標的 %氏模數尚之觀點而言，較佳為65at%以上且95at%以下，尤 其以75at°/〇以上且85at%以下更佳。 又’從上述觀點而言，前驅物組成物中第二烷氧基矽烷化 合物之Si原子組成百分率較佳亦為5站％以上且遍％以下， 尤其以10at%以上且30at%以下更佳。 此外，若為使用四乙氧基石夕燒作為第一烧氧基石夕烧化合 物’且使用雙(三乙氧基石夕燒)乙醇作為第二烧氧基魏化合物 之情況，較佳係四乙氧基石夕烧的Si原子組成百分率為 7 5 at% 以上且8遍以下，雙(三乙氧基魏)乙烧之別原子組成百分 率為15at%以上且25at%以下。此係因為四乙氧基魏間之聚 15 201124487 口開始皿度、雙(二乙氧基石夕燒)乙烧間之聚合開始溫度、四乙 氧基碎烧與雙(二乙氧基梦燒)乙垸之共聚合開始溫度的差異 大，從可湘溫度調絲魏財雜造之觀點而言為極佳。 其-人’針對上述多孔質二氧化矽膜之前驅物組成物的製作 方法、以及使㈣前驅物喊物之乡孔質膜的細方法進行說 明。 於上述(d)非水性溶媒之任一者中，以(a)第一烷氧基矽烷 化合物、〇)第二院氧基矽烧化合物以及⑹非離子性界面活性 劑微胞之比成為上述最佳比例之方式予以混合，例如於25。〇 下擾拌30分鐘。接著，加入屬於⑹反應觸媒之酸觸媒，於例 如25 C下擾拌3小時。其後，加入中和該賴媒之鹼，並攪 =例如24小時，藉此可獲得上述多孔質膜之前驅物組成物。 前驅物組成物較佳係於常溫下為液體。 其次，將如此製作之前驅物組成物塗佈於成膜對象。於例 如屬於成膜對象之矽基板等上，以例如12〇〇rpm之條件，以旋 塗法塗佈上述前驅物組成物。在經如此塗佈於基板之前驅物組 成物所構成之膜内，係形成非離子性界面活性劑微胞，於各微 胞粒子之周圍’集合著第一烧氧基石夕坑化合物或第二烧氧基石夕 燒化合物。 接著，從塗佈於基板之前驅物組成物中，去除非水系溶 媒。例如將塗佈有前驅物組成物之基板於真空環境下加熱，例 如以35秒鐘升溫至35〇°C ,使前驅物組成物中之非水性溶媒 蒸發。用於加熱基板之時間，只要設定為前驅物組成物所含有 之非水性溶媒可揮發之時間即可。 201124487 接著’在非水性溶媒之蒸發的同時、或於非水性溶媒之蒸 發後’開始第一院氧基石夕烧化合物之聚合、第二烧氧基石夕烧化 合物之聚合、以及第一烷氧基矽烷化合物與第二烷氧基矽烷化 合物之共聚合。例如由外部對基板賦予熱，當其溫度到達35〇°C 左右時，前驅物組成物内之第一烷氧基矽烷化合物及第二烷氧 基矽烷化合物亦被賦予熱能量，而使第一烷氧基矽烷化合物之 聚合、第二烷氧基矽烷化合物之聚合、以及第一烷氧基矽烷化 合物與第二烷氧基矽烷化合物的共聚合進行。此外，於該等之 反應中，上述反應觸媒會促進反應。又，利用加熱使非水性溶 媒完全蒸發，則被聚矽氧烷骨架所構成之有機矽氧化物所包圍 之微胞係留存於其位置。 然後，隨著烷氧基矽烷化合物之聚合開始、或者在烷氧基 石夕烧化合物之聚合後，開始非離子性界面活性劑微胞之去除。 例如在與聚合條件相同之溫度下且真空環境下，以照度為 40mW/cm2等條件，例如照射20秒鐘之i72nm的紫外線，而 去除塗佈在基板上的非離子性界面活性劑。亦即，紫外線照射 之時間’係可設定為可去除基板上之非離子性界面活性劑的時 間。若如此對基板實施紫外線照射，則非離子性界面活性劑之 會合狀態或者非離子性界面活性劑本身被紫外線破壞，藉此而 使非離子性界面活性劑微胞從基板上去除。另外，該等加熱處 理及紫外線照射處理並不限於真空環境，於氮環境或含氧環境 等下亦可實施。又，經由紫外線照射處理之結束而形成多孔質 二氧化賴後’柯II由職纽f二氧化賴之表面暴露於 六曱基二矽氮烷之蒸氣中，而進一步實施對多孔質二氧化矽臈 17 201124487 表面之矽烷基化處理。 [實施例] 使用上述各種化合物，製作多孔質二氧化矽膜之前驅物組 成物，將其塗佈於基板之表面，形成實施例之多孔質二氧化矽 膜。之後，測定該實施例之多孔質膜的介電係數以及作為機械 強度指標之楊氏模數，並且測定對多孔質二氧化矽膜施行反應 性乾式蝕刻處理後之介電係數。 於前驅物組成物之製作中，首先係將上述第一烷氧基矽烷 化合物、第二烷氧基矽烷化合物以及非離子性界面活性劑添加 至非水系溶媒中，於25t:下攪拌3G分鐘。接著，加人酸觸媒， 於25 C下授拌3小時後，加入中和酸觸媒之驗，搜拌％小時。 於利用如此製作之前驅物組成物成膜多孔質二氧化矽膜 時，首先，以1200rpm之條件，將該前驅物組成物旋塗於矽基 板表面。將該塗佈有前驅物組成物之基板載置於真空環境下， 將咖度以35秒鐘升溫至35G°C。接著，於3號下照射照度為 40mW/cm2且具有i72nm波長之紫外線2〇秒鐘。 以橢圓測厚儀測定如此形成之多孔質二氧化石夕膜之膜 厚，從使用水銀探針法測定之c_v舰與膜厚，算出介電係 另方面’ 5亥多孔質膜之楊氏模數係利用奈米愿痕試驗機 (nanoindenter，Nanoinstrument 公司製)而測定。 然後，以下述所示之條件，對上述多孔質二氧化賴施行 ^敍刻處理。另外’該處理係使用實施_感絲合電浆之 電漿蝕刻的裝置。 敍刻氣體 CF4(90sccm)，Ar(10sccm；) 201124487 •飯刻氣體之總壓l.OPa .Sl'4〇3(〇CH3)10 (2) The first alkoxylated compound is formed by the dealcoholization polymerization reaction between two or more molecules of a monomer or a polymer constituting the same, and the above chemical formula (1) is formed. One of the polyoxyalkylene skeletons shown (refer to the following chemical formula (3)). (3) R - [0-Si]a - or (3) (b) Second alkoxy decane compound The first alkoxy squid compound is at the two ends of the linear saturated hydrocarbon skeleton with 201124487 having a trialkoxy group. The alkylene group is generalized by the following chemical formula (4). (R) 3 S i - (CH2)x -si (0R) 3 (4) The number of carbon atoms constituting the lower standard x (that is, the linear saturated hydrocarbon skeleton) in the chemical formula (4) is preferably 1 to 3. The alkoxy group of the trialkoxyalkylene group preferably has 1 to 3 ° carbon atoms. The range of the linear saturated hydrocarbon skeleton and the alkoxy group is also arbitrary. Further, the second alkoxydecane compound may be used singly or in combination of two or more kinds. As such a second alkoxydecane compound, for example, bis(trimethoxydecane)methane, bis(triethoxysulfonium)methane, bis(tripropoxydecane)methane, bis(trimethoxyxanthine) Burning) ethane, bis(triethoxysulfonium)ethane, bis(tripropoxydecane)ethane, bis(trioxodecane)propane, bis(triethoxyxanthine)propane, Bis(tripropoxydecane)propane, etc. The first alkoxydecane compound forms a skeleton represented by a part of the above formula (1) by generating two or more intermolecular dealcoholization polycondensation reactions, and P is surrounded by a column of linear saturated hydrocarbons. The composition of the clip is used as a structural unit of the bone transfer specification (9). Correction, between the first-slit-based Wei compound and the second-recorded Wei compound, by the occurrence of two social molecules = alcohol riding reaction, (4) into the chemical formula (1) as a structural skeleton. (Chemical 5) R-[〇_Si-(CH2)x-Si]b, (5) (c) Nonionic surfactant microcapsules 11 201124487 Ethyl acetate, fatty acid polyoxyethylene acetal, The fatty acid is polyoxidized and extended to ethyl sorbitol, and the polyglycol polyoxyethylene extended ethylene adduct is used. Further, it is also possible to use a bismuth, a bismuth, a fatty acid polyglyceride or the like which is generally referred to as a polyhydric alcohol type. Such a nonionic surfactant-active ship utilizes hydrophobicity between molecules of the surfactant in a non-aqueous solvent in which (8) an oxo-oxygen compound or (b) a second alkoxy-based compound is dissolved. The system meets to form a woven fabric that belongs to a spherical structure. The hydrophobic base of the heterozygous community is toward the cell, and the heterophilic interface of the molecule is formed on the outer surface of the cell. Further, the nonionic surfactant microcell system has a temperature characteristic which is structurally destroyed at a temperature at which the first alkoxydecane compound or the second alkoxydecane compound is copolymerized. Then, if the micelle is formed in a non-aqueous solvent in which the first alkoxylate compound or the second alkoxydecane compound is dissolved, by electrostatic interaction with the 'first alkoxy smoldering compound or the first The di-oxo-oxygenated compound will collect around the micelle. Thus, if the above polycondensation reaction is carried out in a state where the first alkoxydecane compound or the second alkoxydecane compound is collected around the micelle, the first alkoxydecane compound and the second alkoxy group The copolymerization system of the decane compound is formed in such a manner as to surround the micelles. Then, the micelles are removed from the copolymer of the first alkoxydecane compound and the second alkoxydecane compound, and pores are formed in the region where the micelles are present. The diameter of the pores thus formed is proportional to the molecular weight of the nonionic surfactant, so that a larger molecular weight surfactant may be selected when the pore diameter is larger. On the other hand, In the case where the pore diameter is small, a surfactant having a smaller molecular weight may be selected. Thus, 12 201124487 non-ionic interface · _ function as a frequency of light holes. (4) Non-aqueous solvent '° The above precursor species are used in addition to the above-mentioned alkoxy-based compound, the first-alkoxy-based compound, and the non-material green spheroid, to dissolve the Non-aqueous solvent. The water-reducing solvent is an alcohol-based, a propylene-based, a fluorene-based, a hydrazine-based system, and a hydrazine-based system, which is removed from the precursor composition before the above-mentioned polymerization reaction, and is more than 75 C. Less than 13 (). (A solvent for the non-aqueous solvent. For example, an alcohol-based alcohol can be used. (Buddha: 78.4. 〇, a methyl ethyl hydrazine belonging to the _ system (Buddha: 79.6. 〇, methyl isobutyl) Ketone (boiling point: 116 kiss and methyl positive top boiling point: 127 ° C), belongs to _ κ dioxygen orchard (boiling point: Xianbu and the ester-based acetic acid isobutyl S) (Buddha: 118. With n-propyl acetate (boiling point: ]. 〇 2 ° C), n-butyl vinegar acetate (Buddha point: 125) 26 ΐ:) (e) Reaction catalyst The above precursor composition, in addition to these various compounds As a reaction catalyst, a catalyst which promotes the condensation reaction of the above-mentioned first-alkoxy-wei compound and the second alkoxy compound, or a rib to adjust the polymerization initiation temperature can be used as the reaction catalyst. In the case of the touch, a dilute acid is exemplified. In addition, in order to neutralize the precursor composition by adding the thinner, and to adjust the pH, a test such as trimethylammonium hydroxide may be added. If the composition of the precursor formed by the above composition is heated to the vicinity of the boiling point of the non-aqueous solvent, the precursor composition is promoted. Evaporation of the non-aqueous solvent contained in the precursor composition, the first alkoxydecane compound and the second alkoxydecane compound are collected around the nonionic surfactant microcells. If further, the first 13 201124487 is driven. When the composition is heated to a temperature at which the first alkoxydecane compound and the second alkoxydecane compound start copolymerization, an organic tantalum oxide film having a polysiloxane skeleton as a main skeleton is formed, and the organic tantalum oxide film is formed in the organic tantalum oxide film. Containing a nonionic surfactant microcell. Then, if the precursor composition is heated to a temperature above the copolymerization of the first alkoxydecane compound and the second alkoxydecane compound, the organic oxidization film The nonionic surfactant microcapsules are destroyed, and voids are formed in the space occupied by the microvesicles. Therefore, the porosity of the porous ceria film having the polyoxynitride skeleton as a main skeleton (ie, The dielectric constant is also determined by the content of the nonionic surfactant microcells. At this time, the organic diterpene compound having a linear saturated hydrocarbon skeleton is used as the second alkoxylate. a decane compound, except that the surface layer of the porous cerium oxide film naturally contains a saturated hydrocarbon, and the saturated hydrocarbon skeleton is also contained in the poly-steam skeleton of the three-site skeleton. The foot is contained in the porous oxidizing frequency. In the form of the Jushixi Oxygen Burning County Towel, the neohydrogen dioxide cap is pre-saturated to the hydrocarbon skeleton. In addition, the neodymium dioxygenation membrane gives a saturated hydrocarbon skeleton with high hydrophobicity. The result is 'g卩In the case of the dry-type side treatment, the bond between the saturated hydrocarbon group and the slave is cut off, and the bond between the April frame and the Shi Xizhi is not easily cut off due to the surname. Therefore, the decrease in hydrophobicity in the porous oxidized lanthanum can be suppressed, and the dielectric constant of the porous SiO2 can be inhibited from being added after the processing. The alkoxy or alkyl carbon of the π 犋 犋In the original addition, the intermolecular distance between the alkoxylated compounds is generally longer than the portion in which the pores are removed, and it is difficult to promote densification of the film. In the case of the above-mentioned porous dioxygenation frequency, since the pores of the porous dioxins ί 201124487 (also the dielectric constant of the porous cerium oxide film) are ensured by the content of the non-surfactant micelles, The portion of the void is removed and no further voids are required. From the viewpoint of ensuring the hardness of the porous ceria film or the hydrophobic f in the protective film, it is preferred to promote the densification. From this point of view» as the first alkoxy sinter compound, preferably a tetramethoxy oxime, a tetraethoxy decane, a methyl phthalate belonging to a polymer of tetradecyl decane, a dimethyl group Dimethoxydecane, and dimethyldiethoxydecane. Further, the alkoxy group in the second alkoxy decane compound is preferably an alkoxy group having a carbon number of K3. According to the constitution, the portion in which the pores are removed can be promoted, so that the mechanical strength of the porous dioxide film is more or less, and the hydrophobic group in the film is actually protected. Further, the percentage of the Si atomic composition ratio of the first alkoxydecane compound in the precursor composition is as large as the length of the poly-weiweizi-laid or the expansion of the three T, and is used as a porous dioxide-compensating compound. From the viewpoint of the % modulus of the mechanical hardness index, it is preferably 65 at% or more and 95 at% or less, and more preferably 75 at / 〇 or more and 85 at % or less. Further, from the above viewpoint, the Si atomic composition percentage of the second alkoxydecane compound in the precursor composition is preferably 5 stations% or more and 8% or less, more preferably 10 at% or more and 30 at% or less. Further, in the case where tetraethoxy cerium is used as the first alkoxylated compound and bis (triethoxy sulphur) ethanol is used as the second alkoxy compound, it is preferred to be tetraethoxy. The Si atomic composition percentage of the base stone is 75 5 at% or more and 8 times or less, and the atomic composition percentage of bis(triethoxy Wei)ethane is 15 at% or more and 25 at% or less. This is because the polymerization temperature of the starting point of the 201124487 mouth of the tetraethoxy group, the polymerization start temperature of the bis(diethoxy sulphide), the tetraethoxy sinter and the bis (diethoxy dream) The difference in the starting temperature of the copolymerization of acetamidine is large, and it is excellent from the viewpoint of the temperature of the xiangxiang temperature regulating silk. The method of producing the precursor composition of the above-mentioned porous ceria film and the method of making the cell membrane of the precursor of the precursor are described. In any of the above (d) non-aqueous solvent, the ratio of (a) the first alkoxydecane compound, the ruthenium second oxy oxime compound, and (6) the nonionic surfactant nucleus becomes the above Mix the best ratios, for example at 25. Shake the mixture for 30 minutes. Next, an acid catalyst belonging to the (6) reaction catalyst is added, and the mixture is scrambled for 3 hours, for example, at 25 C. Thereafter, the base of the solvent is neutralized and stirred for, for example, 24 hours, whereby the porous film precursor composition can be obtained. The precursor composition is preferably a liquid at normal temperature. Next, the precursor composition thus prepared was applied to a film formation object. For example, the precursor composition is applied by spin coating on a crucible substrate or the like which is a film formation target, for example, at a condition of 12 rpm. In the film formed by the composition of the precursor before being coated on the substrate, nonionic surfactant micelles are formed, and the first alkoxylated compound or the second is collected around the respective microparticles. Alkoxylate is burned. Next, the non-aqueous solvent is removed from the precursor composition applied to the substrate. For example, the substrate coated with the precursor composition is heated in a vacuum atmosphere, for example, by raising the temperature to 35 ° C for 35 seconds to evaporate the non-aqueous solvent in the precursor composition. The time for heating the substrate may be set to a time during which the non-aqueous solvent contained in the precursor composition is volatilizable. 201124487 Next, 'the evaporation of the non-aqueous solvent or after the evaporation of the non-aqueous solvent' begins the polymerization of the first compound oxy-stone compound, the polymerization of the second alkoxylate compound, and the first alkoxy group. Copolymerization of a decane compound with a second alkoxydecane compound. For example, heat is applied to the substrate from the outside, and when the temperature reaches about 35 ° C, the first alkoxy decane compound and the second alkoxy decane compound in the precursor composition are also imparted with thermal energy, so that the first The polymerization of the alkoxydecane compound, the polymerization of the second alkoxydecane compound, and the copolymerization of the first alkoxydecane compound and the second alkoxydecane compound are carried out. Further, in the above reactions, the above reaction catalyst promotes the reaction. Further, when the non-aqueous solvent is completely evaporated by heating, the microcellular system surrounded by the organic cerium oxide composed of the polyoxyalkylene skeleton remains at its position. Then, the removal of the nonionic surfactant micelles begins with the initiation of the polymerization of the alkoxydecane compound or after the polymerization of the alkoxylated compound. For example, at a temperature similar to the polymerization conditions and under a vacuum atmosphere, the non-ionic surfactant coated on the substrate is removed under the conditions of an illuminance of 40 mW/cm 2 or the like, for example, by irradiating ultraviolet rays of i72 nm for 20 seconds. That is, the time of ultraviolet irradiation can be set to the time at which the nonionic surfactant on the substrate can be removed. When the substrate is irradiated with ultraviolet rays in this manner, the nonionic surfactant is brought into contact with each other or the nonionic surfactant itself is destroyed by ultraviolet rays, whereby the nonionic surfactant micelles are removed from the substrate. Further, the heat treatment and the ultraviolet irradiation treatment are not limited to a vacuum environment, and may be carried out in a nitrogen atmosphere or an oxygen-containing atmosphere. Further, after the completion of the ultraviolet irradiation treatment, the porous diazonium is formed, and the surface of the keel II is exposed to the vapor of hexamethylene diazoxide, and the porous cerium oxide is further applied.臈17 201124487 Surface oxime alkylation treatment. [Examples] Using the above various compounds, a porous ceria film precursor composition was prepared and applied to the surface of a substrate to form a porous ceria film of the example. Thereafter, the dielectric constant of the porous film of this example and the Young's modulus as a mechanical strength index were measured, and the dielectric constant after the reactive dry etching treatment was performed on the porous ceria film. In the preparation of the precursor composition, the first alkoxydecane compound, the second alkoxydecane compound, and the nonionic surfactant are first added to a nonaqueous solvent, and stirred at 25t for 3G minutes. Next, add acid catalyst, and mix for 3 hours at 25 C, add neutral acid catalyst test, and mix for % hours. When the porous ceria film was formed by using the precursor composition thus prepared, the precursor composition was spin-coated on the surface of the ruthenium substrate at 1200 rpm. The substrate coated with the precursor composition was placed under a vacuum atmosphere, and the temperature was raised to 35 G ° C for 35 seconds. Next, ultraviolet rays having an illuminance of 40 mW/cm2 and having a wavelength of i72 nm were irradiated for 2 sec seconds under No. 3. The film thickness of the porous dioxide dioxide film thus formed was measured by an elliptical thickness gauge, and the C_v ship and the film thickness measured by the mercury probe method were used to calculate the Young's mode of the dielectric system. The number was measured using a nanoindenter (manufactured by Nanoinstrument Co., Ltd.). Then, the above porous ruthenium oxide was subjected to a sinter treatment under the conditions shown below. Further, this treatment was carried out using a device for performing plasma etching of a sensitized plasma. Gas engraved CF4 (90sccm), Ar (10sccm;) 201124487 • Total pressure of cooking gas l.OPa.
•天線功率800W •偏移功率500W 以上述條件進行乾式蝕刻處理後，測定多孔質二氧化矽膜 之膜厚，並且算出介電常數。另外’多孔質二氧化矽膜之膜厚 測定方法與介電常數之算出方法，係與該多孔質二氧化矽膜之 触刻前相同。 [實施例1] 將上述(a)〜(e)所示之各種化合物以及(f)pH調整劑，以下述配 方混合’製作上述多孔質二氧化矽膜之前驅物組成物。 (a) 第一烷氧基矽烷化合物：四乙氧基矽烷0024莫耳(mol) (b) 第二烷氧基矽烷化合物：雙(三曱氧基石夕烧)乙烷0.0048莫 耳(mol) (c) 非離子性界面活性劑：EPAN45〇(商品名，第一工業製藥 股份有限公司製，參照化學式(6))0.00084莫耳(m〇1) (化6) HO (CH2CH2〇)i3 (CH (CH3) CH2〇)2Q (CH2CH2〇)i3H …⑹ (d) 非水系溶媒：乙醇33ml (e) 反應觸媒：硝酸溶液 (f) pH調整劑：氫氧化三乙基銨/丙二醇單甲基醚溶液〇.〇〇〇〇7 莫耳(mol)/75ml 另外，上述前驅物組成物中之上述四乙氧基矽烷的Si原 子組成比百分率為83at%’而該前驅物組成物中之上述雙(三曱 氧基石夕烧)乙燒之Si原子組成比百分率為17at%。 201124487 使用上述前驅物組成物形成多孔質二氧化矽膜後，測定其 膜厚、^電常數以及楊氏模數，膜厚為151nm，介電常數為 .1揚氏模數為6.0GPa。又’以上述條件對該多孔質二氧化 石夕膜施行賦_處理後，敎料及介電常數，膜厚為 11111介電吊數為3.1。亦即，藉由乾式钱刻處理之實施， 多孔質二氧化石夕膜之介電常數上升了 1.〇。 [實施例2] 將上述(a)〜(e)所示之各種化合物以及⑵阳調整劑，以下述配 方混合’製作上述多孔質二氧切膜之_物組成物。 (a)第一烷氧基矽烷化合物：甲基矽酸鹽〇 〇〇83莫耳 ⑼第：烧氧基石夕烧化合物：雙(三曱氧基石夕院)乙烧〇.〇〇42莫 耳(mol) (c)非離子性界面活性劑：EPAN45〇(商品名)〇 〇〇42莫耳 (Φ非水系溶媒··乙醇13.3ml (e) 反應觸媒：硝酸溶液(0.5%)514g (f) pH s周整劑：氫氧化三曱基録/丙二醇單甲基醚溶液〇 〇_4 莫耳(mol)/l 96.2ml 另外，上述前驅物組成物中之上述甲基石夕酸鹽的別原子 組成比百分率為66at%’而該前驅物組成物中之上述雙(三甲氧 基石夕烧)乙烧之Si原子組成比百分率為34at%。 使用上述前驅物組成物形成多孔質二氧化矽膜後，測定其 膜厚、介電常數以及楊氏模數，膜厚為152nm，介電常數為 2.0，揚氏模數為5.8GPa。又，以上述條件對該多孔質二氧化 矽膜施行乾式蝕刻處理後，測定臈厚及介電常數，臈厚為 20 201124487 l〇3nm，介電常數為2.9。亦即，藉由乾式蝕刻處理之實施， 多孔質二氧化矽膜之介電常數上升了 〇9。 [比較例1] 於上述[實施例1]、[實施例2]之(a)〜(f)所示之各種化合物 中，不添加第二烷氧基矽烷化合物，製作多孔質膜之前驅物組 成物。 (a)第一烧氧基矽烷化合物：四乙氧基矽烷〇 〇24莫耳(m〇1) (c) 非離子性界面活性劑：EPAN450(商品名)〇.0006莫耳(m〇1) (d) 非水系溶媒：乙醇20ml (e) 反應觸媒：硝酸溶液(〇.5%)15g (f) pH „周整劑.氫氧化二甲基銨/丙二醇單甲基喊溶液〇 00005 莫耳(moiy54ml 使用上述前驅物組成物形成多孔質二氧化矽膜後，測定其 膜厚、介電常數以及楊氏模數，膜厚為191nm，介電常數為 2·0 ’揚氏模數為6.5GPa。又，以上述條件對該多孔質二氧化 矽膜施行乾式蝕刻處理後，測定膜厚及介電常數，膜厚為 102nm ’介電常數為3 8。亦即，藉由乾式侧處理之實施， 多孔質二氧化碎膜之介電常數上升了 1.8。 如此’實施例中乾式蝕刻處理後之介電常數之上升平均為 0.95 ’另-方面，比油巾乾式侧處理後之介電常數的上升 為U。亦即’在上述實施例中，藉由使構成多孔質二氧化石夕 展之聚錄財架巾含有飽和烴骨架，即便在施行乾式儀刻處 理後’仍可抑制烴基之脫離，可說是抑制了介f常數之上升。 又，實施例之揚氏模數為6.GGPa、5.8GPa，認為與比較例之 21 201124487 楊氏模數大致相同。因此，即便為在聚石夕氧烧骨架中賦予直鏈 飽和烴之形態，只要直鏈飽和烴之碳原子數為1〜3，三燒氧基 矽烷基中之各烷氧基的碳原子數為1〜3，則可確保多孔質膜之 機械強度，或更確實地保護疏水基。 如以上所說明’根據上述實施形態’可獲得以下列舉之效 果。 (1) 使多孔質二氧化矽膜之前驅物組成物含有第一烷氧基石夕 烧化合物、第二烧氧基石夕烧化合物、以及在第一烧氧基石夕烧化 合物與第二烷氧基矽烷化合物發生共聚合之溫度以上會被破 壞的非離子性界面活性劑微胞。藉此，在第一烷氧基矽烷化合 物與第二烷氧基矽烷化合物發生共聚合之條件下，會形成以聚 矽氧烷骨架作為主骨架之有機矽氧化膜，於該有機矽氧化膜中 係含有非離子性界面活性劑微胞。然後，在第一烷氧基矽烷化 合物與第二烷氧基矽烷化合物發生共聚合之溫度以上，有機矽 氧化膜中所含之非離子性界面活性劑微胞被破壞，於該微胞所 佔有之空間，形成空孔。因此，以聚矽氧烷骨架作為主骨架之 多孔質膜之空孔率，亦即介電常數，係由非離子性界面活性劑 微胞之含有量所決定。 (2) 使用於直鏈飽和烴之兩末端具有三烷氧基矽烷基之烷氧 基夕燒化σ物，作為第二烧氧基石夕烧化合物。藉此，於構成多 孔質二氧化石夕膜之單位骨架内，係含有該第二烷氧基矽院化合 物所具有之直鏈麵和烴。@此，在對纽質二氧化频應用 乾式飯刻處理之情況，即便上述直鏈飽和烴之任—者與鄰接於 此之原子之間的鍵結被切斷，仍可抑制烴基之脫離。又，由於 22 201124487 如此抑制烴之脫離’故可容易修復該烴與鄰接於其之原子間的 鍵結。因此，可抑制因烴之脫離所造成之水分子的吸附，進而 可抑制多孔質二氧化矽膜加工後之介電常數的增加。 (3) 第一烧氧基石夕燒化合物係從由四曱氧基石夕烧、四乙氧基石夕 烧、屬於四甲氧基石夕烷之聚合體的曱基矽酸鹽、二曱基二甲氧 基矽烷、以及二曱基二乙氧基石夕烷所組成群組中選擇之至少一 者。亦即’藉由具有碳數為1或2之烷氧基的烷氧基矽烷化合 物而形成多孔質二氧化矽膜。藉此，在去除了空孔之部分係促 進膜之緻密化，故可確保多孔質二氧化矽膜之機械強度，或更 確實地保護膜中之疏水基。 (4) 於直鏈飽和烴之兩末端具有烷氧基矽烷基之第二烷氧基 矽烷化合物的各烷氧基，係碳數1〜3之烷氧基。藉此，在去除 了空孔之部分係促進膜之緻密化，故可確保多孔質二氧化石夕膜 之機械強度’或更確實地保護膜中之疏水基。 (5) 第二烧氧基梦烧化合物之物質量，係定在提升多孔質二氧 化矽膜之疏水性且不降低該多孔質二氧化矽膜之機械強度的 範圍，亦即大於第一烧氧基石夕烧化合物所含之石夕的物質量之 5〇/〇且未滿50%之範圍内。藉此，可兼顧確保利用由第二烧氧 基矽烷化合物對多孔質二氧化矽膜賦予之疏水性，並抑制該多 孔質二氧化矽膜之機械強度的降低。 以上說明本發明之實施形態，但本發明並不限定於上述内 容’亦可在申請專利範圍及均等者之範圍内進行變化。 23• Antenna power: 800 W • Offset power: 500 W After dry etching treatment under the above conditions, the film thickness of the porous ceria film was measured, and the dielectric constant was calculated. Further, the method for measuring the film thickness of the porous ceria film and the method for calculating the dielectric constant are the same as those before the contact of the porous ceria film. [Example 1] The porous ceria film precursor composition was prepared by mixing the various compounds shown in the above (a) to (e) and (f) the pH adjuster with the following formula. (a) First alkoxy decane compound: tetraethoxy decane 0024 mol (mol) (b) second alkoxy decane compound: bis(trimethoxy oxalate) ethane 0.0048 mol (mol) (c) Nonionic surfactant: EPAN45〇 (trade name, manufactured by Daiichi Kogyo Co., Ltd., refer to chemical formula (6)) 0.00084 mol (m〇1) (chemical 6) HO (CH2CH2〇)i3 ( CH (CH3) CH2〇)2Q (CH2CH2〇)i3H (6) (d) Non-aqueous solvent: ethanol 33ml (e) Reaction catalyst: nitric acid solution (f) pH adjuster: triethylammonium hydroxide / propylene glycol monomethyl Alkali ether solution 〇.〇〇〇〇7 mol (mol) / 75 ml Further, the above-mentioned tetraethoxy decane in the above precursor composition has a Si atomic composition ratio of 83 at%' and is in the precursor composition The Si atomic composition ratio of the above bis(trioxane oxy-stone) was 6.17%. 201124487 After forming a porous ceria film using the above precursor composition, the film thickness, electro-conductivity, and Young's modulus were measured, and the film thickness was 151 nm, and the dielectric constant was .1 Young's modulus was 6.0 GPa. Further, after the porous silica dioxide film was subjected to the above-mentioned conditions, the material and dielectric constant were as follows, and the film thickness was 11111. That is, the dielectric constant of the porous dioxide dioxide film is increased by 1. [Example 2] The various compounds shown in the above (a) to (e) and (2) a positive adjusting agent were mixed with the following formula to prepare the composition of the above porous dioxic film. (a) First alkoxy decane compound: methyl phthalate 〇〇〇 83 mol (9) No.: alkoxy sulphide compound: bis (trioxane oxy shi xiyuan) 乙 〇 〇 〇〇 42 莫(mol) (c) Nonionic surfactant: EPAN 45 〇 (trade name) 〇〇〇 42 mol (Φ non-aqueous solvent · ethanol 13.3 ml (e) Reaction catalyst: nitric acid solution (0.5%) 514 g ( f) pH s week conditioning agent: tridecyl hydroxide hydroxide / propylene glycol monomethyl ether solution 〇〇 _4 mol (mol) / l 96.2ml In addition, the above methyl chloride compound in the above precursor composition The atomic composition ratio of the atomic ratio is 66 at%', and the Si atomic composition ratio of the above bis (trimethoxy sulphur) E-burning in the precursor composition is 34 at%. The porous precursor is formed by using the above precursor composition. After the ruthenium film, the film thickness, dielectric constant, and Young's modulus were measured, and the film thickness was 152 nm, the dielectric constant was 2.0, and the Young's modulus was 5.8 GPa. Further, the porous ruthenium dioxide film was subjected to the above conditions. After the dry etching treatment, the thickness and the dielectric constant were measured, and the thickness was 20 201124487 l 〇 3 nm, and the dielectric constant was 2.9. That is, by dry type. The dielectric constant of the porous cerium oxide film was increased by 〇9. [Comparative Example 1] Various kinds of (a) to (f) shown in the above [Example 1] and [Example 2] In the compound, a second alkoxy decane compound is not added to prepare a porous film precursor composition. (a) First alkoxy decane compound: tetraethoxy decane 〇〇 24 mol (m〇1) ( c) Nonionic surfactant: EPAN450 (trade name) 0006.0006 mol (m〇1) (d) Non-aqueous solvent: ethanol 20ml (e) Reaction catalyst: nitric acid solution (〇.5%) 15g ( f) pH „周整剂. Dimethylammonium hydroxide/propylene glycol monomethyl sputum solution 〇00005 Moer (moiy54ml) After forming a porous cerium oxide film using the above precursor composition, the film thickness and dielectric constant were measured. And a Young's modulus, a film thickness of 191 nm, a dielectric constant of 2·0', and a Young's modulus of 6.5 GPa. Further, the porous ceria film is subjected to dry etching treatment under the above conditions, and then the film thickness is measured. The dielectric constant, the film thickness is 102 nm, and the dielectric constant is 38. That is, by the implementation of the dry side treatment, the dielectric constant of the porous dioxide film is The increase in the dielectric constant after the dry etching treatment in the embodiment is 0.95'. On the other hand, the increase in the dielectric constant after the dry side treatment of the oil towel is U. That is, in the above embodiment. In the case where the polycrystalline carbon dioxide frame constituting the porous silica stone is contained in a saturated hydrocarbon skeleton, even after the dry etching treatment is performed, the detachment of the hydrocarbon group can be suppressed, and the increase in the dielectric constant can be suppressed. Further, the Young's modulus of the examples was 6.GGPa and 5.8 GPa, which was considered to be substantially the same as the 21 201124487 Young's modulus of the comparative example. Therefore, even if a linear saturated hydrocarbon is imparted to the polyoxo skeleton, as long as the linear saturated hydrocarbon has 1 to 3 carbon atoms, the number of carbon atoms of each alkoxy group in the tris-oxyalkylene group is When it is 1 to 3, the mechanical strength of the porous film can be ensured, or the hydrophobic group can be more reliably protected. As described above, the effects listed below can be obtained by the above embodiment. (1) The porous ceria film precursor composition contains a first alkoxylate compound, a second alkoxylate compound, and a first alkoxylate compound and a second alkoxy group. Nonionic surfactant micelles which are destroyed above the temperature at which the decane compound is copolymerized. Thereby, under the condition that the first alkoxydecane compound and the second alkoxydecane compound are copolymerized, an organic tantalum oxide film having a polysiloxane skeleton as a main skeleton is formed, and the organic tantalum oxide film is formed in the organic tantalum oxide film. Contains nonionic surfactant micelles. Then, at a temperature at which the first alkoxydecane compound and the second alkoxydecane compound are copolymerized, the nonionic surfactant microcapsules contained in the organic tantalum oxide film are destroyed, and the micelles are occupied. The space creates voids. Therefore, the porosity of the porous film having the polysiloxane skeleton as the main skeleton, that is, the dielectric constant is determined by the content of the nonionic surfactant microcapsules. (2) An alkoxylated yttrium oxide having a trialkoxyalkylene group at both ends of a linear saturated hydrocarbon as a second alkoxylated compound. Thereby, the linear surface of the second alkoxy broth compound and the hydrocarbon are contained in the unit skeleton constituting the porous corrosive oxide film. @This, in the case of the dry rice engraving treatment of the neodymium dioxide, even if the bond between any of the linear saturated hydrocarbons and the atom adjacent thereto is cut, the detachment of the hydrocarbon group can be suppressed. Further, since 22 201124487 thus inhibits the detachment of hydrocarbons, it is easy to repair the bond between the hydrocarbon and the atom adjacent thereto. Therefore, adsorption of water molecules due to detachment of hydrocarbons can be suppressed, and an increase in dielectric constant after processing of the porous cerium oxide film can be suppressed. (3) The first alkoxylated compound is a mercapto citrate or a dimethyl dimethyl hydride which is a polymer of tetramethoxy cerium, tetraethoxy cerium, tetramethoxy oxalate. At least one selected from the group consisting of oxydecane and dimercaptodiethoxy oxalate. That is, a porous ceria film is formed by an alkoxydecane compound having an alkoxy group having 1 or 2 carbon atoms. Thereby, the densification of the film is promoted in the portion where the voids are removed, so that the mechanical strength of the porous ceria film can be ensured or the hydrophobic groups in the film can be more surely protected. (4) Each alkoxy group of the second alkoxy decane compound having an alkoxyalkyl group at both ends of the linear saturated hydrocarbon is an alkoxy group having 1 to 3 carbon atoms. Thereby, the densification of the film is promoted in the portion where the pores are removed, so that the mechanical strength of the porous silica film or the hydrophobic groups in the film can be surely protected. (5) The mass of the second alkoxy compound is determined to increase the hydrophobicity of the porous ceria film without reducing the mechanical strength of the porous ceria film, that is, greater than the first burning The content of the material of the cerium oxide compound is 5 〇 / 〇 and less than 50%. Thereby, it is possible to ensure both the hydrophobicity imparted to the porous ceria film by the second pyrithione compound and the decrease in the mechanical strength of the porous ceria film. The embodiments of the present invention have been described above, but the present invention is not limited to the above-described contents, and may be changed within the scope of the claims and the scope of the claims. twenty three