509997 A7 ____ B7_^___ 五、發明説明（1 ) 技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於多孔質SOG膜之製作方法，特別係關於 使有機矽烷進行加水分解，並於界面活性劑之存在下加熱 處理，來製作多孔質SOG膜之方法。 技術背景 近年來，與於LSI領域中導入銅（Cu )或鋁（A1 )等 之配線一起，進行關於配線構造或層間絕緣膜等之硏究開 發。由於僅使用Cu等之配線來有效地減少配線延遲會有困 難’從半導體製程中所謂使用低比介電率氧化物膜（Sl〇2 膜）作爲層間絕緣膜，進一步得到比介電率低之薄膜的觀 點’則提案使該氧化物膜成爲多孔質。例如，提案利用傳 統之SOG ( spin on glass )之塗布法，以無機SOG之矽烷 化來形成低比介電率之多孔質Si〇2膜。又，亦提案利用電 漿CVD，使用有機矽烷來電漿聚合，而形成低比介電率之 多孔質Si〇2膜。 經濟部智慧財產局員工消費合作社印製 在以傳統之方法來形成SiCh膜之後，於CVD步驟等之 半導體製程中，於其上進一步層合薄膜，則有所謂比介電 率上升之問題。在使用無機S〇G而形成多孔質Si〇2膜的情 況下，孔洞直徑變得過大，難以形成細微孔洞並使比介電 率値變低，.又，在使用有機矽烷而形成多孔質Si〇2膜的情 況下，薄膜品質不足，又，亦有所謂耐熱溫度低（4 5 0 °C 以下）的問題。 因此’本發明係解決上述傳統技術之缺點者，爲低比 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4- 509997 A7 B7 五、發明说明（2 ) (請先閱旗背面之注意事項再填寫本頁) 介電率之層間絕緣膜，其第1目的爲提供以該層間絕緣膜 形成後之CVD製程等，即使於其上進一步層合薄膜，比介 電率亦不變之多孔質SOG膜的製作方法（第1發明）。 又，以上述傳統之方法所得之多孔質膜的特性方面， 由於肇因於該多孔質性之吸濕性而吸附水分，並使A1等之 配線被腐蝕’爲了改善該吸濕性’提案於以疏水性之CH3 基等來置換殘留於多孔質膜之親水基OH基，同時以酸化處 理OH基而形成^〇2，來使孔洞內部之膜表面疏水化的化學 處理方法。 即使在以形成低比介電率之層間絕緣膜後之CVD步驟 等，於其上進一步層合其他薄膜時，比介電率亦不變之多 孔質SOG膜之製作方法的情況下，所得之多孔質Si〇2膜， 經濟V智慧財產局員工消費合作社印製 由於垂直於基板地配向該孔洞，而有從膜表面而來之水蒸 氣等之水分入侵之問題。又，無機SOG膜係包含多量之〇H 基，即使燒成後亦殘留未反應之OH基。因此，氛圍氣體中 之水分吸附於該殘留之〇H基，而有所謂腐蝕A1等配線之 問題。另外，上述化學處理亦有所謂該製程控制困難之問 題。 因而，本發明係爲了解決從如上述之膜表面而來之水 蒸氣等的水分入侵、吸濕問題，爲防止從膜表面而來之水 分的侵入、.抑制吸濕之低比介電率之層間絕緣膜，其第2 目的爲提供以該層間絕緣模型成後之CVD步驟等，即使進 一步於其上層合薄膜，比介電率亦不變之多層多孔質S〇G 膜或單層多孔質SOG膜之製造方法（第2發明）。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 509997 A7 _B7_ 五、發明説明（3 ) (請先閱讀背面之注意事項再填寫本頁) 又本發明係於殘留如上述之未反應OH基的情況下，由 於從多孔質SOG膜除去殘留OH基，而爲低比介電率之層間 絕緣膜，其第3目的爲提供以該層間絕緣膜形成後之CVD _步驟等，即使進一步於其上層合薄膜，比介電率亦不變之 多層多孔質SOG膜或單層多孔質SOG膜之製造方法（第3 發明）。 另外本發明係爲了解決所謂殘留如上述之未反應OH基 的問題，爲至少在孔洞內部之壁面不存在OH基之低比介電 率之層間絕緣膜，其第4目的爲提供以該層間絕緣膜形成 後之CVD步驟等，即使進一步於其上層合薄膜，比介電率 亦不變之多層多孔質SOG膜或單層多孔質SOG膜之製造方 法（第4發明）。 【發明之說明】 經濟部智慧財產局員工消費合作社印製 本發明者等，由所謂層間絕緣膜之比介電率以低的範 圍爲佳的觀點來看，爲了以旋轉塗布法來得到低介電率之 多孔質SOG膜，選擇各種材料，並進行爲了發現適當材料 及反應條件之專心一意的硏究開發。其結果爲以添加界面 活性劑於使用有機矽烷之反應系統，即爲比介電率低的多 孔質Si〇2膜，成功地於膜形成後之半導體製程中，得到即 使進一步於其上形成層合膜，比介電率亦不變的多孔質 Si〇2膜，而達成本發明之第1目的。 .第1發明之多孔質SOG膜製作方法係由以使用包含有 機矽烷、水、及醇類之有機係烷液，使該有機矽烷進行酸 i紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ' ~ -6 - 509997 A7 _ _B7___ 五、發明説明（4 ) 加水分解或鹼加水分解，並於界面活性劑之存在下加熱處 理而得多孔質Si⑴膜所構成。 —--------4^衣-- i m (請先閱讀背面之注意事項再填寫本頁) 又，本發明者等，爲了抑制從如上述所得之多孔質 Si〇2膜表面之水蒸氣等之水分的入侵、吸濕之專心一意的 .開發硏究。其結果爲以添加界面活性劑於使用有機矽烷之 反應系統中而得到多孔質SiCh膜，其次，以至少重複一次 該步驟，並於該步驟中所得之多孔質以〇2膜上進一步形成 多孔質Si〇2膜而形成多層狀態，或，以介存特定之疏水性 膜於各多孔質膜之間，或，以特定之疏水性膜覆蓋，即被 覆多孔質表面，S卩爲比介電率低之多孔質Si〇2膜，成功地 於膜形成後之半導體製程中，得到郎使進一步於其上形成 層合膜，比介電率亦不變之經疏水化之多孔質Si〇2膜，而 達成本發明之第2目的。 經濟部智慧財產局員工消費合作社印製 第2發明之多孔質SOG膜製作方法係由至少重複一次 得到前述多孔質Si〇2膜之第1步驟，並於該第1步驟所得之 多孔質Si〇2膜上進一步依次形成多孔質31〇2膜所構成。以 多層地層合該等多孔質膜來抑制多孔質膜之吸濕，同時可 於後段步驟之半導體製程中，得到即使於其上形成層合膜 ，比介電率亦不變之多孔質Si〇2膜。以層合方式，以互相 交錯垂直於基板來配向之孔洞狀態來重疊各個薄膜，由於 最上層膜中之孔洞與最下層膜中之孔洞間大致上形成未連 接，於多層膜中大致上沒有貫通孔洞，該結果爲抑制了層 合後之多孔質膜的吸濕。 又，於前述第1步驟所得之多孔質Si〇2膜表面上，以 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " ' ' 509997 A7 ___ B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) CVD法或濺鍍法來形成SiO:膜、膜或SiChNy膜之任一 種’亦可進行覆蓋表面之第2步驟，或者，亦可進一步重 複至少一次該第1步驟及第2步驟。在以該等疏水性膜進一 步覆蓋之單層多孔質膜的情況下，或，在多層之多孔質膜 .的情況下’與不以疏水性膜覆蓋之多孔質膜比較，進一步 抑制水分之侵入、吸濕，同時於後段步驟之半導體製程中 ’即使於其上形成層合膜，比介電率亦不變。 再者，本發明者等’進行爲了除去如上述所得之多孔 質Si〇2膜之殘留〇H基之專心一意的開發硏究。其結果爲以 添加界面活性劑於使用有機矽烷之反應系統中而得到多孔 質31〇2膜，其次，以針對多孔質Si〇2膜進行氧電漿處理、 電子射線照射處理或紫外線照射處理之任一種，成功地除 去殘留於該多孔質膜之未反應0H基，即爲比介電率低之多 孔質以〇2膜，於膜形成後之半導體製程中，得到即使進一 步於其上形成層合膜，比介電率亦不變之疏水化後之多孔 質3丨〇2膜，而達成本發明之第3目的。 經濟部智慧財產局員工消費合作社印製 第3發明之多孔·質S0G膜製作方法係由以使用包含有 機矽烷、水、及醇類之有機係烷液，使該有機矽烷進行酸 加水分解或鹼加水分解、於界面活性劑之存在下加熱處理 而得多孔質Si〇2膜，其次，以氧電漿處理、電子射線照射 處理或紫外線照射處理之任一種來處理，除去殘留於該多 孔質Si〇2膜之未反應〇H基所構成。該〇H基之除去係以上 述處理而引起下述反應之目的。 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） -8 - )1)9997 A7 B7 五、發明説明（6 )509997 A7 ____ B7 _ ^ ___ V. Description of the invention (1) Technical field (please read the notes on the back before filling out this page) The present invention relates to the method for making porous SOG membranes, and particularly to the hydrolytic decomposition of organic silanes. A method for producing a porous SOG film by heat treatment in the presence of a surfactant. Technical background In recent years, research and development on wiring structures, interlayer insulating films, and the like have been conducted along with the introduction of copper (Cu), aluminum (A1), and the like into the LSI field. It is difficult to effectively reduce the wiring delay by using only wiring such as Cu. From the so-called low-dielectric-constant oxide film (S102 film) as an interlayer insulating film in the semiconductor manufacturing process, a further lower dielectric constant is obtained. From the viewpoint of thin film, it is proposed to make the oxide film porous. For example, it is proposed to use a conventional SOG (spin on glass) coating method to silylate inorganic SOG to form a porous Si02 film with a low specific permittivity. In addition, it is also proposed to form a porous Si0 2 film with a low specific permittivity by using plasma CVD and using an organic silane to polymerize the plasma. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. After forming the SiCh film by the traditional method, and further laminating the film in a semiconductor process such as a CVD step, there is a problem of a so-called increase in specific permittivity. When a porous SiO2 film is formed using inorganic SOG, the pore diameter becomes too large, it is difficult to form fine pores, and the specific permittivity 値 is reduced. Furthermore, porous Si is formed using an organic silane. In the case of 〇2 film, the film quality is insufficient, and the so-called heat-resistant temperature is low (less than 450 ° C). Therefore, the present invention addresses the shortcomings of the above-mentioned traditional technology, and applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) for the paper ratio of this paper at a lower ratio. -4-509997 A7 B7 V. Description of the invention (2) (please first Please read the notes on the back of the flag and fill in this page again.) The first purpose of the interlayer insulating film of dielectric rate is to provide a CVD process after the formation of the interlayer insulating film. Even if a thin film is further laminated on it, the specific permittivity A method for producing a porous SOG film that does not change (first invention). In addition, in terms of the characteristics of the porous membrane obtained by the above-mentioned conventional method, moisture is absorbed due to the porous hygroscopicity and the wiring of A1 and the like is corroded. A chemical treatment method in which the hydrophilic OH group remaining in the porous membrane is replaced with a hydrophobic CH3 group, etc., and the OH group is treated with an acid to form ^ 02 to hydrophobize the membrane surface inside the pores. Even in the case of a CVD step after forming an interlayer insulating film with a low specific permittivity, etc., when other thin films are further laminated thereon, the specific permittivity of the porous SOG film is not changed. Porous SiO2 film, printed by the Consumer Cooperative of the Economic V Intellectual Property Bureau, because the holes are aligned perpendicular to the substrate, there is a problem of water intrusion from the surface of the film, such as water vapor. In addition, the inorganic SOG film contains a large amount of 0H groups, and unreacted OH groups remain even after firing. Therefore, moisture in the ambient gas is adsorbed on the remaining 0H groups, and there is a problem that wirings such as A1 are corroded. In addition, the above-mentioned chemical treatment also has a problem that the control of the process is difficult. Therefore, the present invention is to solve the problem of moisture intrusion and moisture absorption from water vapor and the like from the film surface, to prevent moisture intrusion from the film surface, and to suppress the low specific permittivity of moisture absorption. The second purpose of the interlayer insulating film is to provide a multilayer porous SOG film or a single layer porous film that does not change the specific permittivity even if a thin film is further laminated thereon, such as a CVD step after forming the interlayer insulating model. Method for manufacturing SOG film (second invention). This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 509997 A7 _B7_ V. Description of the invention (3) (Please read the precautions on the back before filling this page) The invention is based on the residual In the case of the above-mentioned unreacted OH group, the residual OH group is removed from the porous SOG film, and it is an interlayer insulating film with a low specific permittivity. The third purpose is to provide a CVD after the formation of the interlayer insulating film. For example, even if a thin film is further laminated thereon, the manufacturing method of a multilayer porous SOG film or a single-layer porous SOG film that does not change the specific permittivity (third invention). In addition, the present invention is to solve the problem of the so-called unreacted OH groups remaining as described above, and is an interlayer insulating film having a low specific permittivity that does not have OH groups at least on the wall surface inside the hole. The fourth object is to provide the interlayer insulation. A method for manufacturing a multilayer porous SOG film or a single-layer porous SOG film that has a specific dielectric constant that does not change even if a thin film is further laminated thereon, such as a CVD step after film formation (4th invention). [Explanation of the invention] The inventors of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperative printed this inventor. From the viewpoint that the so-called dielectric constant of the interlayer insulating film is preferably in a low range, in order to obtain a low dielectric by a spin coating method, Various materials are selected for the porous SOG membrane with a specific electric capacity, and research and development have been carried out in order to find suitable materials and reaction conditions. As a result, by adding a surfactant to a reaction system using an organic silane, that is, a porous Si02 film having a lower specific dielectric than that of a porous SiO2 film, it was successfully used in a semiconductor process after the film was formed, and a layer was formed thereon. The composite film is a porous Si02 film with a constant specific permittivity, which achieves the first object of the present invention. The first method of producing a porous SOG film is to use an organic alkane solution containing an organic silane, water, and alcohol to make the organic silane perform acid paper. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X) 297 mm) '~ -6-509997 A7 _ _B7___ 5. Description of the invention (4) Hydrolysis or alkali hydrolysis, and heat treatment in the presence of a surfactant to form a porous Si⑴ film. —-------- 4 ^ 衣-im (Please read the precautions on the back before filling this page) In addition, the present inventors, etc., in order to suppress the surface of the porous Si〇2 film obtained as described above. The invasion of moisture such as water vapor and moisture absorption are devoted to development. As a result, a porous SiCh film was obtained by adding a surfactant to a reaction system using an organic silane. Secondly, this step was repeated at least once, and the porous material obtained in this step was further formed into a porous film on the 02 film. SiO2 film to form a multi-layer state, or a specific hydrophobic film is interposed between each porous film, or a specific hydrophobic film is covered, that is, the porous surface is covered, and S 卩 is the specific permittivity The low porous SiO2 film was successfully used in the semiconductor manufacturing process after the film was formed to form a laminated film on top of the porous SiO2 film, and the specific dielectric constant was not changed. To achieve the second purpose of the invention. The manufacturing method of the porous SOG film printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the second invention is to repeat the first step of obtaining the porous SiO2 film at least once, and obtain the porous Si obtained in the first step. A porous 3102 film was formed on the two films in this order. The porous films are laminated in multiple layers to suppress the moisture absorption of the porous films, and at the same time, in the semiconductor manufacturing process in the subsequent steps, porous Si can be obtained without changing the specific dielectric constant even if a laminated film is formed thereon. 2 film. Each film is laminated in a layered manner, with holes oriented in a direction perpendicular to the substrate. The holes in the uppermost film and the holes in the lowermost film are almost unconnected, and there is almost no penetration in the multilayer film. The result is pores, which suppresses moisture absorption of the porous film after lamination. In addition, on the surface of the porous SiO2 film obtained in the first step, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied at the paper size. &Quot; '' 509997 A7 ___ B7 V. Description of the invention (5 ) (Please read the precautions on the back before filling in this page) CVD method or sputtering method to form SiO: film, film or SiChNy film. 'The second step of covering the surface can also be performed, or it can be repeated further. The first step and the second step are performed at least once. In the case of a single-layer porous film further covered with such a hydrophobic film, or in the case of a multi-layer porous film, the invasion of moisture is further suppressed compared with a porous film not covered with a hydrophobic film. , Moisture absorption, in the semiconductor process at the same time, even if a laminated film is formed on it, the specific dielectric constant will not change. In addition, the present inventors and the like have conducted intensive development research in order to remove the remaining 0H groups of the porous SiO2 film obtained as described above. As a result, a porous 3 10 2 film was obtained by adding a surfactant to a reaction system using an organic silane, and then a porous Si 0 2 film was subjected to oxygen plasma treatment, electron beam irradiation treatment, or ultraviolet irradiation treatment. Either one of the unreacted 0H groups remaining in the porous film is successfully removed, that is, a porous film with a lower dielectric constant than the SiO 2 film. In the semiconductor process after the film is formed, a layer is formed even further thereon. The composite film is a porous 3 SiO 2 film with a specific dielectric constant that is not changed, thereby achieving the third object of the present invention. The third method for producing a porous SOG film printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is to use an organic alkane solution containing an organic silane, water, and alcohols to perform acid hydrolysis, or alkali decomposition of the organic silane. A porous Si0 2 film is obtained by hydrolyzing and heating in the presence of a surfactant, and then treated with any one of an oxygen plasma treatment, an electron beam irradiation treatment, or an ultraviolet irradiation treatment to remove the remaining residual Si. The 〇2 film is composed of unreacted OH groups. The removal of the OH group is for the purpose of causing the following reaction by the above-mentioned treatment. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -8-) 1) 9997 A7 B7 V. Description of Invention (6)
(OSiOH ) 2O -> 2 Si〇2 + H2O (請先閲讀背面之注意事項再填寫本頁) 由於以上述反應除去殘留之〇H成爲H2◦，而變成不會吸附 氛圍氣體中的水分於多孔質膜，而得到比介電率低之多孔 .質膜，進一步抑制A1等之配線的腐蝕。又，該疏水性多孔 質SiO:膜係於後段步驟之半導體製程中，即使於其上形成 層合膜，比介電率亦不變。 另外，本發明者等，進行爲了得到不存在殘留未反應 〇H基之多孔質Si〇2膜之專心一意的開發硏究。其結果爲在 以添加界面活性劑於使用有機矽烷之反應系統而得到多孔 質Si〇2膜時，以於二個步驟進行加熱處理，成功地使多孔 質膜變成疏水性，即爲比介電率低的多孔質SiCh膜，於膜 形成後之半導體製程中，得到即使於其上形成層合膜，比 介電率亦不變之疏水性多孔質Si〇2膜，而達成本發明之第4 目的。 經濟部智慧財產局g(工消費合作社印製 第4發明之多孔質SOG膜製作方法係由以使用包含有 機矽烷、水、及醇類之有機係烷液，使該有機矽烷進行酸 加水分解或鹼加水分解、於界面活性劑之存在下加熱處理 而得多孔質Si〇2膜的方法，首先，以於蒸發該水與醇類之 溫度下進行之第一加熱處理步驟，其次升溫，於以該界面 活性劑之疏水部分（以下，稱爲疏水基）覆蓋所得之多孔 質Si〇2膜之至少孔洞內部之壁面的溫度來進行之第二加熱" 處理步驟所構成。因此，由於多孔質膜之孔洞內部之壁面 變成疏水性，氛圍氣體中之水分不會吸附於多孔質膜，而 本紙張尺度適用中國國家標準（CNS ) A4規格（210X2517公釐） -9 - 509997 A7 __B7 五、發明説明（7 ) 得到比介電率低之多孔質膜，進一步抑制A1等之配線的腐 蝕。又，該疏水性多孔質SiCh膜係於後段步驟之半導體製 程中，即使於其上形成層合膜，比介電率亦不變。於以疏 水基覆蓋前述孔洞內部之壁面中，並蒸發以水、醇類爲主 .之溶劑後，以於350〜450 °C之溫度進一步燒成爲佳。未滿 3 50 °C則難以降低比介電率，又，超過450 °C則界面活性劑 會過度蒸發，所得之多孔質膜則不能得到疏水基，同時恐 怕會破壞膜構造。 再省，根據第1發明，混合有機矽烷、水、醇類、及 酸或鹼，將進一步添加界面活性劑之有機矽烷液於半導體 基板上，並加熱處理，以蒸發該水’、醇類、界面活性劑， 可得多孔質Si〇2膜。根據第2發明，於上述加熱處理所得 之多孔質Si〇2膜的表面上，以CVD法或濺鍍法，形成SiOz 膜、SiNx膜或Si〇xNy膜之任一種，以覆蓋該表面之步驟， 或，以進一步重複至少一次該加熱處理步驟及該覆蓋步驟 並形成多層膜的步驟，可得多孔質Si〇2膜。根據第3發明 ’針對於上述加熱處理所得之多孔質Si〇2膜進行氧電漿處 理、電子射線照射處理或紫外線照射處理之任一種，可除 去殘留於該多孔質SiCh膜之未反應〇H基，並得到疏水性多 孔質Si〇2膜。根據第4發明，以首先於200〜3 50 °C之溫度處 理上述加熱處理，其次，於350〜450 °C之溫處理蒸發以水及 醇類爲主之第一加熱處理步驟，以於所得之多孔質Si〇2膜 之至少孔洞內部之膜表面上附著界面活性劑之親水部分（ 以下，稱爲親水基）的狀態來結束膜形成，並以該界面活 本紙張尺度適用中國國家標準（CNS ) A4規格（21 O X 297公釐） I-------^^衣-- « * (請先閲讀背面之注意事項再填寫本頁) U訂 經濟部智慧財產局員工消费合作社印製 -10 - 509997 A7 __________B7_ 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 性劑之疏水基覆蓋該孔洞內部之壁面的第二加熱處理步驟 來進行，可得疏水性多孔質Si〇2膜。因此，適度地蒸發界 面活性劑，並使至少孔洞內部之壁面變成疏水性。 於上述第1〜4發明中所用之有機矽烷係如TEOS (四甲 基鄰矽酸鹽）、TMOS (四甲氧基矽烷）等之可加水分解之 有機矽氧烷；界面活性劑係陽離子性界面活性劑、特別以 如氯化月桂基三甲基銨、氯化正十六烷基三甲基銨、溴化 院基三甲基錢、氯化十六院基三甲基鏡、溴化十六院基三 甲基錢、氯化十八院基三甲基錢、氯化院基二甲基乙基錢 、溴化烷基二甲基乙基銨、溴化十六烷基二甲基乙基銨、 溴化十八烷基二甲基乙基銨、或氯化甲基月桂基苯基三甲 基銨等之鹵化烷基三甲基銨系陽離子性界面活性劑爲佳。 經濟部智慧財產局員工消f合作社印製 又，各原料之使用量係以相對於有機矽烷1·莫耳，使 用水8〜1 5莫耳、用於酸加水分解或鹼加水分解之酸或鹼 〇. 5〜1 · 5莫耳、界面活性劑〇. 1〜〇. 4莫耳爲佳。水未滿8莫耳 則所得之膜的比介電率不爲會變小，超過1 5莫耳則會析出 Si〇2固體。酸或鹼未滿〇.5莫耳則不能進行既定之反應，超 過1.5莫耳則反應系統會凝固。界面活性劑未滿〇.1莫耳則 薄膜之比介電率會變高，超過〇 · 4莫耳則薄膜性質會變差。 還有，醇類係爲了調整反應液全體所添加者，針對反應液 之黏性，由於容易塗佈，調節該量來添加。 【圖示之簡單說明】 第1圖係依照本發明之爲了氧電漿處理所用之處理室 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 509997 A7 _B7___ 五、發明説明（9 ) 之模型剖面圖。 第2圖係 (請先閲讀背面之注意事項再填寫本頁) (A )針對依照傳統技術所得之多孔質SiO:膜之剖面 的掃描型電子顯微鏡（SEM )攝影； (B )針對依照本發明所得之多孔質Si〇2膜之剖面的 掃描型電子顯微鏡（SEM )攝影。 第3圖係依照本發明所得之多孔質膜之FT-IR光譜。 【用於實施發明之最佳型態】 根據第1發明之多孔質SOG膜製作方法，使用包含有 機矽烷、水、及醇類之有機矽烷液’，將添加界面活性劑於 以使該有機矽烷進行酸加水分解或鹼加水分解所得之液體 者，塗佈於半導體基板上，於界面活性劑之存在下加熱， 蒸發水、醇類、界面活性劑之同時，又，在包含其他有機 物質等於反應系統的情況下，以除去該物質來製作多孔質 Si〇2膜。隨著界面活性劑之蒸發，於膜內產生多數的空隙 部分（空隙率：約60 %以上），因而得到多孔質膜。 經濟部智慧財產局員工消费合作社印製 原料矽烷方面，如果爲如上述之可分解之有機矽氧烷 ’並無特別限制來使用。醇類方面，如果爲乙醇、異丙醇 等之醇系溶劑，並無特別限制來使用。加水分解係以酸來 加水分解，亦可以鹼加水分解，爲了該加水分解，可使用 硝酸或鹽酸等之無機酸、蟻酸等之有機酸、氨等之鹼。界 面活性劑方面，以使用如上述鹵化烷基三甲基銨系陽離子 性界面活性劑爲佳。其他界面活性劑方面，亦可使用例如 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 509997 A7 B7 五、發明説明（10 ) (請先閱讀背面之注意事項再填寫本頁) 氯化二甲基癸基苯基銨、氯化二乙基十二烷基苯基銨、溴 化三甲基十二烷基銨、溴化烯丙基二丁基十二烷基銨、氯 化二乙基丙銅基十二院基錢等。 原料之使用量係如上所述，相對於原料有機矽烷1莫 耳，水方面以8〜15莫耳，酸或鹼方面以0.5〜1.5莫耳，界面 活性劑方面以0.1〜0.4莫耳爲佳。以適當地選擇該界面活性 劑之使用量與加熱處理條件，可選擇性地製作具有所希望 之比介電率之多孔質SiCh膜。 經濟部智慧財產局員工消費合作社印製 將如上述所得之有機矽烷液，以通常之旋轉塗布法等 之塗佈方法塗佈於半導體基板上，其次使用公認之紅外線 加熱爐等來加熱處理、蒸發水-醇系溶劑、以及界面活性劑 之其他有機物質等，來製作多孔質Si〇2膜。該情況之加熱 處理條件如果爲蒸發該溶劑及界面活性劑等，並可得到多 孔質膜的條件，則並無特別之限制。爲了得到比介電率低 之多孔質膜，以首先於空氣中以200〜3 50 °C範圍之溫度來處 理並蒸發溶劑，其次，於例如100〜10_5Pa範圍之真空中，可 蒸發界面活性劑之其他有機物質等之溫度（例如250〜500 °C ，以350〜440 °C爲佳，以3 80〜4 5 0 QC爲特佳），不會破壞所 得之多孔質膜構造之時間的處理爲佳。 針對該等所得之多孔質Si〇2膜，蒸鍍鋁電極之電極並 測定比介電率，了解得到符合本發明目的之多孔質SOG膜 。即，得到比介電率低，又，於SOG模型成後之半導體製 程中，即使於其上層合薄膜但是大致上無比介電率上升的 層間絕緣膜。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ~ -13- 509997 A 7 B7 五、發明説明（11 ) 如上所述，以使用TEOS、TMOS等之有機矽烷爲佳， 並可製作例如空隙率60 %以上之低介電率之層間絕緣膜。 (請先閱讀背面之注意事項再填寫本頁) 由於空隙率變高，例如達到80 %之範圍，對於基於構成絕 緣膜材料之物性的比介電率之影響變少，由於受到空氣影 ，響之支配，而得到低比介電率之層間絕緣膜。由該等之觀 點來看，亦可使用可加水分解烷氧化物來取代有機矽烷， 在與有機矽烷相同之情況下，可製作作爲低比介電率之層 間絕緣膜的多孔質膜。該等院氧化物方面，使用例如 Ti (〇C3H7 ) 4、Zr (〇C4H9 ) 4等之屬於週期表4A族之Τι 、Zr等之烷氧化物而得。 經濟部智慧財產局員工消費合作社印¾) 根據第2發明之多孔質SOG膜製作方法之一實施型態 ，至少重複一次得到如上述之多孔質Si〇2膜的步驟（第一 步驟），並於以第一步驟所得之多孔質Si〇2膜上進一步形 成多孔質Si〇2膜。隨著界面活性劑之蒸發，於膜內產生多 數之空隙部分（空隙率：約60 %以上），因而得到多孔質 膜，又，由於使該多孔質膜形成多層膜而抑制水分之入侵 ，可改良吸濕性。於該情況下，多孔質膜之所層合的絕緣 膜變得過厚，則有所謂逆向於向薄膜化之方向前進之半導 體製程技術的趨勢問題。因而，以考慮可抑制吸濕性之膜 厚同時儘量變薄者爲佳。雖然重複多次該等第一步驟，但 是於該情況下，必須設定比較於由上述第1發明之情況的 單層所構成各多孔質膜膜厚之多孔質膜厚更薄者。例如， 雙層之多孔質膜的情況下，以設定各多孔質膜之膜厚於0.5 # m範圍爲佳。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐〉 -14- 509997 A7 ___B7 五、發明説明（12 ) (請先閱讀背面之注意事項再填寫本頁) 原料矽烷、醇類、加水分解用的酸及鹼、以及界面活 性劑方面，可使用與上述第1發明相同者。又，上述原料 之使用量係以上述之範圍爲佳。以適當地選擇界面活性劑 之使用量與加熱處理條件，可選擇性地形成具有所希望之 比介電率之Si〇2膜的多層膜。 將如上述所得之有機矽烷液以通常之旋轉塗布法之塗 佈方法塗佈於半導體基板上，至少重複一次製作如上述所 處理之多孔質Si〇2膜的步驟，形成多孔質膜。該情況之加 熱處理條件係如上所述。 經濟部智慧財產局員工消費合作社印製 對於該等所得之多孔質SiCh膜，針對由如下之膜側面 之吸濕性來進行確認試驗。在製作於Si基板上之多孔質 Si〇2膜上面，以聚醯亞胺膜被覆於側面。切下以聚醯亞胺 被覆之2個樣本之一者之樣本的四邊，並使多孔質Si〇2膜 之剖面出現。以原來之被覆狀態，以及以針對出現多孔質 Si〇2膜之剖面之同一條件來進行吸濕試驗，在比較試驗後 之比介電率中觀察有否從多孔質Si〇2膜側面而來之吸濕。 該結果爲由於認爲以聚醯亞胺被覆之原來樣本，與切下側 面並出現多孔質Si〇2膜之剖面的樣本之吸濕試驗後的比介 電率沒有差別，了解於多孔質Si〇2膜之側面沒有孔洞的出 口，且該多孔質Si〇2膜之孔洞垂直配向於基板。 又，根據第2發明之其他實施型態，以上述第一步驟 所得之多孔質膜上’以CVD法或濺鍍法，來形成例如膜厚 100nm以下之疏水性的Si〇2膜、SiN,膜或SiO*Ny膜之任一 種，並進行覆蓋該多孔質膜表面。覆蓋層之膜厚過厚’則 本紙張尺度適用中國画家揉準（CNS ) A4規格（210X297公釐） -15- 509997 A7 ______ B7 五、發明説明（13 ) (請先閲讀背面之注意事項再填寫本頁) 作爲所覆蓋之絕緣膜的總膜厚容易變厚，而有所謂逆向於 向薄膜化之方向前進之半導體製程技術的趨勢問題。因而 ’以考慮可抑制吸濕性之膜厚同時儘量變薄者爲佳。覆蓋 層可爲單層，亦可爲複數層。其次，如所希望，可重複該 等第一步驟並於該覆蓋層上進一步形成多孔質膜，又，亦 可多次重複該等之第一步驟及覆蓋層形成步驟。亦於該情 況下，與前述第一實施型態之情況相同地，必須設定比較 於由上述第1發明之情況的單層所構成各多孔質膜膜厚及 覆蓋層之膜厚之多孔質膜厚更薄者。例如，雙層之多孔質 膜與雙層之覆蓋膜的情況下，以設定各多孔質膜於0.5 ν m 範圍、各覆蓋層於50nm範圍爲佳。’由以特定之疏水性膜來 覆蓋該等多孔質膜可抑制水分之侵入。 原料矽烷、醇類、加水分解用之酸及鹼、以及界面活 性劑方面，可使用與上述相同者。又，上述原料之使用量 以在上述之範圍者爲佳。以適當地選擇界面活性劑之使用 量與加熱處理條件，可選擇性地製作具有所希望之比介電 率之疏水性Si〇2膜。· 經濟部智慧財產局員工消费合作社印製 將如上述所得之有機矽烷液以通常之旋轉塗布法之塗 佈方法塗佈於半導體基板上，並製作如上述所處理之多孔 質SiCh膜。該情況之加熱處理條件係如上所述。 對於該等所得之多孔質Si〇2膜’與上述相同地，進行 針對由如下之膜側面之吸濕性之確認試驗。該結果爲由於 認爲以聚醯亞胺被覆之原來樣本，與切下側面並出現多孔 質Si〇2膜之剖面的樣本之吸濕試驗後的比介電率沒有差別 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -16- 509997 A7 _______B7_ 五、發明説明（14 ) ’ 了解於多孔質SiCh膜之側面沒有孔洞的出口，且該多孔 質Si〇2膜之孔洞垂直配向於基板。 (請先閱讀背面之注意事項再填寫本頁) 針對依照第2發明所得之多孔質31〇2膜，蒸鍍鋁極等 之電極並測定比介電率，了解得到符合本發明目的之多孔 質SOG膜。即，得到無水分侵入於多孔質膜、吸濕性改良 、比介電率低之多孔質SOG膜。再者，對於疏水化處理後 之多孔質SOG膜，於半導體製程中，得到即使以CVD法等 於其上層合其他薄膜，大體上亦無多孔質Si〇2膜之比介電 率之上升的層間絕緣膜。 根據第2發明，以使用TEOS或TMOS等之有機矽烷爲 佳’於與第1情況相同地，可製作具有高空隙率之低比介 電率的層間絕緣膜。亦可使用與第1發明相同之矽烷氧化 物來取代有機矽烷。 經濟部智慧財產局員工消費合作社印^ 根據第3發明之多孔質SOG膜製作方法之一實施型態 ’得到如上述之多孔質Si〇2膜，其次，以氧電漿處理、電 子射線照射處理或紫外線照射處理之任一種，來除去殘留 於所得之多孔質SiCh膜之未反應OH基。隨著界面活性劑之 蒸發，於膜內產生多數之空隙部分（空隙率：約50 %以上 )’因而得到多孔質膜，以針對該多孔質膜來進行上述疏 水化處理’來除去殘留OH基，可抑制氛圍氣體中之水分的 吸附，得到表面改質後之疏水性多孔質S ◦ G膜。 原料矽烷、醇類、加水分解用的酸及鹼、以及界面活 性劑.方面，可使用與上述第1發明相同者。又，上述原料 之使用量係以上述之範圍爲佳。以適當地選擇界面活性劑 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐） -17- 509997 A7 B7 五、發明説明（15 ) 之使用量與加熱處理（燒成處理）條件，可適宜地製作具 有所希望之比介電率之疏水性多孔質Si〇2膜。 (請先閱讀背面之注意事項再填寫本頁) 將如上述所得之有機矽烷液以通常之旋轉塗布法之塗 佈方法塗佈於半導體基板上，並製作如上述所處理之多孔 質SiO:膜。該情況之加熱處理條件係如上所述。 對於如上述所得之多孔質Si〇2膜，於與第2發明之情 況相同地，進行針對由膜側面之吸濕性之確認試驗。該結 果爲由於認爲以聚醯亞胺被覆之原來樣本，與切下側面並 出現多孔質Si〇2膜之剖面的樣本之吸濕試驗後的比介電率 沒有差別，了解於多孔質Si〇2膜之孔洞，垂直配向於基板 〇 經濟部智慧財產局員工消費合作社印製 其次，針對上述多孔質SiCh膜進行氧電漿處理、電子 射線照射處理或紫外線照射處理並使多孔質膜疏水化。此 時所發生之反應係由於伴隨著脫水，通常之情況下，多孔 質膜會收縮，雖然恐怕會在薄膜上產生裂痕，但是由於以 本發明所得之多孔質膜有50 %以上之孔洞率，因爲該薄膜 構造本身會吸收因上述反應之應力的產生，所以未觀察到 薄膜裂痕等之現象。 關於疏水化處理，以下說明氧電漿處理作爲代表例。 氧電漿處理係以利用通常之微波放電之氧電漿處理裝 置來進行而得。即，如第1圖所示，於處理室1中，設置用 於裝載被處理基板2之基板夾具3，該夾具係具備加熱器等 之加熱手段4。又，於處理室1之側壁係裝設由放電管所構 成之反應性氣體之導入部分5、具備連接於微波電源6之電 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -18- 509997 A7 _______ B7______ 五、發明説明（16 ) 漿產生部分7之氧電漿產生裝置8。該氧電漿產生裝置8係 以微波電源6來使由氣體源9而來之所導入之氧氣或混入少 量之其他氣體（例如，Ar、Kr、Xe等）於其中之氣體的 反應性氣體電漿化，構成將其導入處理室1內。以真空泵 10經由設置於處理室之側壁之真空排氣口 11，將上述處理 室1真空排氣後，裝載於基板夾具3上，針對形成於加熱後 之被處理基板2上之多孔質Si〇2膜來進行氧電漿處理，依 照上述反應式來除去殘留〇H基。即，殘留OH基變成H〇2 ，氣化並從真空排氣口 1 1以真空泵1 〇排氣。該氧電漿處理 係以例如含氧氣體流量100〜2000SCCM、RF及微波電力 300〜3000W、壓力0.5〜2Τοη，進行既定時間而得。 上述電漿產生裝置雖然爲下游型，但亦可利用其以外 之平行平板電極型、ECR型等之電漿產生裝置。電漿化之 激發手段並無特別之限制。再者，上述氧電漿處理以外， 亦可利用可除去多孔質膜之殘留ΟΗ基之處理手段。例如， 相對於多孔質膜，以通常之方法，使用電子射線槍來照射 電子射線，或同時照射紫外線亦可除去殘留〇Η基。 針對該等所得之多孔質SOG膜，蒸鍍鋁極等之電極並 測定比介電率，了解得到符合本發明目的之多孔質SOG膜 。即，得到無水分之吸附、比介電率低之多孔質層間絕緣 膜，即於疏水化處理後之半導體製程中，得到即使更於其 上層合薄膜，大體上亦無比介電率上升的層間絕緣膜。 如上所述，以使用TEOS或TMOS等之有機矽烷爲佳， 於與第1情況相同地，可製作具有高空隙率之低比介電率 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） —-------衣-- * , (請先閱讀背面之注意事項再填寫本頁) 、-5r-m 經濟部智慧財產局員工消費合作社印奴 19- 509997 A7 B7 五、發明説明（17 ) 的層間絕緣膜。亦可使用與第1發明相同之砂氧院來取代 有機矽烷。 根據第4發明之多孔質SOG膜製作方法之一實施型態 ，得到多孔質Si〇2膜時，首先，於空氣中以200〜3 50 t之溫 度進行上述加熱處理’其次，升溫並於空氣氛圍氣體中， 以於真空中爲佳，以3 50〜450 °C (以380〜450 °C爲佳）之溫 度進行。以設定加熱處理氛圍氣體成該等狀態，以疏水基 覆蓋所得之多孔質膜之至少孔洞內部之壁面，同時亦使比 介電率變低。根據該發明，隨著界面活性劑之蒸發，於膜 內產生多數之空隙部分（空隙率：約50 %以上），因而得 到多孔質膜。在孔洞形成之熱處理步驟中，以附著界面活 性劑之親水基於孔洞內部之膜表面的狀態來結束孔洞形成 (即，多孔質膜形成），則界面活性劑之疏水基以朝向相 對於孔洞內部之膜表面之反側面狀態（即，從孔洞內部之 膜表面朝向孔洞空間方向之狀態）存在，以疏水基覆蓋孔 洞內部之壁面。因此，由於至少孔洞內部之壁面變爲疏水 性，可抑制氛圍氣體中之水分的吸附，得到經表面改質之 疏水性多孔質膜。 原料矽烷、醇類、加水分解用的酸及鹼、以及界面活 性劑方面，可使用與上述第1發明相同者。又，上述原料 之使用量係以上述之範圍爲佳。以適當地選擇界面活性劑 之使用量與加熱處理（燒成處理）條件，可適宜地製作具 有所希望之比介電率之疏水性多孔質SiCh膜。 將如上述所得之有機矽烷液以通常之旋轉塗布法之塗 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） —-------— 礞 Μ (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -20- 509997 A7 B7 五、發明説明（18 ) (請先閱讀背面之注意事項再填寫本頁) 佈方法塗佈於半導體基板上，並製作如上述所處理之多孔 質Si〇2膜。該情況之加熱處理條件係以上述溫度條件者爲 佳。即，爲了得到比介電率低之疏水性多孔質膜，首先， 於空氣中以200〜3 50 °C範圍之溫度來處理，並蒸發以水-醇 系爲主之溶劑，其次，於氮氣等之絕對介電率小之氣體氛 圍中，而於以100〜l(T5Pa範圍爲佳之真空中，以可蒸發界面 活性劑之其他有機物質等之溫度，進行不破壞所得之多孔 質膜構造之時間的處理。 針對該等所得之多孔質Si〇2膜，與第2發明之情況相 同地，進行針對從膜側面而來之吸濕性的確認測試。該結 果爲由於認爲以聚醯亞胺被覆之原來樣本，與切下側面並 出現多孔質^〇2膜之剖面的樣本之吸濕試驗後的比介電率. 沒有差別，了解該多孔質Si〇2膜之孔洞，垂直配向於基板 〇 經濟部智慧財產局員工消費合作社印製 針對依照第4發明所得之多孔質膜，蒸鍍鋁電極等之 電極並測定比介電率，了解得到符合本發明目的之疏水性 多孔質SOG膜。即，·無水分之吸附、比介電率低之多孔質 層間絕緣膜，即於疏水化處理後之半導體製程中，得到即 使進一步於其上層合薄膜，大體上亦無比介電率上升的層 間絕緣膜。 如上所述，以使用TEOS或TMOS等之有機矽烷爲佳， 於與第1情況相同地，可製作具有高空隙率之低比介電率 的層間絕緣膜。亦可使用與第1發明相同之矽氧烷來取代 有機矽烷。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 509997 A7 _______B7 五、發明説明（19 ) 針對以本發明所得之上述的多孔質膜，進行以FT — iR分 析之光譜測疋時，無〇 Η基之吸收峰。 (請先閱讀背面之注意事項再填寫本頁) 如於以上述第1〜4發明所得之多孔質膜殘留未反應之 親水性ΟΗ基，對於該多孔質膜，如果進行利用通常之拋光 裝置之氧電漿處理’或者同時進行公認之電子射線槍的電 子射線照射處理或紫外線照射處理，由於可除去殘留ΟΗ基 ’進一步提昇多孔質之疏水性。 【實施例】 以下，參照圖示來說明本發明之實施例。 (實施例1 :第1發明） 經濟部智慧財產局員工消費合作社印製 使用相對於TEOS 1莫耳之硝酸0.7莫耳、HO: 12莫耳 、乙醇1 5莫耳、既定量之界面活性劑，作爲調製用於多孔 質SiOa膜製作之反應液的原料，並調製多孔質S〇G膜之 Si〇2液。添加相對於TOES 1莫耳之0.1、0.15、0.2、0.25 之氯化正十六烷基三甲基銨（關東化學（株）製，商品名 :CTAC1 )作爲界面活性劑，並調製塗佈液。於半導體基 板（試料編號A 1〜H1 )上，以3000轉/分鐘之條件旋轉塗佈 各塗佈液。使用公認之紅外線加熱爐，如於第1表來表示 所塗佈之各基板，最初，於空氣中，以200〜400 °C來處理， 其次於100〜l(T5Pa之氛圍氣體中，以400 °C來燒成處理，得 到多孔質以〇2膜。該情況下，從最初之處理溫度200 °C升 溫至下一步驟之處理溫度400 °C之時間爲60分鐘’其他情 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22- 509997(OSiOH) 2O-> 2 Si〇2 + H2O (Please read the precautions on the back before filling in this page) Because the remaining OH removed by the above reaction becomes H2, it will not adsorb moisture in the atmosphere. Porous film to obtain a porous film with a lower specific dielectric than to suppress the corrosion of wiring such as A1. In addition, the hydrophobic porous SiO: film is used in a semiconductor process in a subsequent step, and even if a laminated film is formed thereon, the specific dielectric constant is not changed. In addition, the present inventors have conducted intensive research and development in order to obtain a porous Si02 film having no remaining unreacted OH groups. As a result, when a porous Si0 2 film was obtained by adding a surfactant to a reaction system using an organic silane, heat treatment was performed in two steps to successfully make the porous film hydrophobic. Porous SiCh film with low rate, in the semiconductor manufacturing process after film formation, even if a laminated film is formed on it, a hydrophobic porous SiO2 film with constant specific dielectric constant is obtained, reaching the first level of the invention. 4 Purpose. The Intellectual Property Bureau of the Ministry of Economic Affairs (the fourth method for manufacturing a porous SOG film printed by the Industrial and Consumer Cooperatives) is to use an organic alkane solution containing an organic silane, water, and alcohols to decompose the organic silane with acid or water. A method for obtaining a porous Si0 2 film by alkali hydrolysis and heat treatment in the presence of a surfactant, first, a first heat treatment step performed at a temperature at which the water and an alcohol are evaporated, and then a temperature increase is performed, followed by The second heating " treatment step is performed by covering the temperature of at least the wall surface inside the pores of the obtained porous Si02 film with a hydrophobic portion (hereinafter, referred to as a hydrophobic group) of the surfactant. This is because the porous material is porous. The wall surface inside the hole of the membrane becomes hydrophobic, and the moisture in the atmosphere will not be adsorbed on the porous membrane. The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X2517 mm) -9-509997 A7 __B7 V. Invention Explanation (7) A porous film with a lower dielectric constant is obtained to further suppress the corrosion of the wiring of A1 and the like. The hydrophobic porous SiCh film is made of a semiconductor in a subsequent step. In the process, even if a laminated film is formed thereon, the specific dielectric constant does not change. After covering the wall surface of the inside of the hole with a hydrophobic group, and evaporating the solvent mainly composed of water and alcohol, the temperature is 350 ~ It is better to burn at a temperature of 450 ° C. It is difficult to lower the specific permittivity below 3 50 ° C, and if the temperature exceeds 450 ° C, the surfactant will evaporate excessively, and the obtained porous film cannot obtain hydrophobic groups. I am afraid that the membrane structure will be damaged. In addition, according to the first invention, an organic silane liquid containing a surfactant is further added to a semiconductor substrate by mixing an organic silane, water, alcohol, and an acid or an alkali, and heat treatment is performed to evaporate the Water ', alcohols, and surfactants can be used to obtain a porous Si0 2 film. According to the second invention, SiOz is formed on the surface of the porous Si 0 2 film obtained by the above-mentioned heat treatment by a CVD method or a sputtering method. Any one of a film, a SiNx film, or a SiOxNy film to cover the surface, or a step of further repeating the heat treatment step and the covering step and forming a multilayer film at least once to obtain a porous SiO2 film . According to the 3rd invention ' The porous SiO2 film obtained by the above heat treatment is subjected to any one of an oxygen plasma treatment, an electron beam irradiation treatment, or an ultraviolet irradiation treatment to remove unreacted 0H groups remaining in the porous SiCh film and obtain hydrophobicity. Porous Si02 film. According to the fourth invention, the above-mentioned heat treatment is firstly treated at a temperature of 200 ~ 3 50 ° C, and secondly, it is treated at a temperature of 350 ~ 450 ° C. The first is mainly water and alcohol. The heat treatment step ends the film formation in a state where a hydrophilic portion (hereinafter, referred to as a hydrophilic group) of a surfactant is adhered to the surface of at least the inside of the pores of the obtained porous Si0 2 film, and the interface is formed at the interface. Paper size applies Chinese National Standard (CNS) A4 specification (21 OX 297 mm) I ------- ^^ clothing-«* (Please read the precautions on the back before filling this page) U-Order Ministry of Economy Printed by the Intellectual Property Bureau Staff Consumer Cooperatives -10-509997 A7 __________B7_ V. Description of the Invention (8) (Please read the precautions on the back before filling this page) The second heat treatment of the hydrophobic base of the sex agent covering the wall surface inside the hole Steps in OK, a hydrophobic porous SiO2 film can be obtained. Therefore, the surfactant is moderately evaporated, and at least the wall surface inside the hole becomes hydrophobic. The organic silanes used in the above-mentioned first to fourth inventions are hydrolyzable organic siloxanes such as TEOS (tetramethyl o-silicate), TMOS (tetramethoxysilane), etc .; the surfactant is cationic Surfactants, such as lauryl trimethyl ammonium chloride, n-hexadecyl trimethyl ammonium chloride, bromide trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, bromide Hexadecyl trimethylchrysene, Hexadecyl trimethylchrysene chloride, Hexadecyl dimethylethylchrysene, Alkyldimethylethylammonium bromide, Hexadecyldimethylbromide Alkyltrimethylammonium-based cationic surfactants such as methylethylammonium, octadecyldimethylethylammonium bromide, or methyllaurylphenyltrimethylammonium chloride are preferred. Printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, the cooperative, and the amount of each raw material used is 1 · mol relative to the organic silane, 8 ~ 15 mol of water, acid or hydrolyzed acid or alkali The base 0.5 ~ 1.5 mole, and the surfactant 0.1 ~ 0.4 mole are preferred. If the water is less than 8 mol, the specific permittivity of the obtained film will not decrease, and if it exceeds 15 mol, a solid SiO 2 will be precipitated. If the acid or base is less than 0.5 mol, the intended reaction cannot be performed, and if it exceeds 1.5 mol, the reaction system will solidify. If the surfactant is less than 0.1 mol, the specific permittivity of the film will become higher, and if it exceeds 0.4 mol, the film properties will be deteriorated. In addition, the alcohol is added to adjust the amount of the reaction solution because it is easy to apply in order to adjust the whole reaction solution. [Brief description of the diagram] Figure 1 is the processing room used for oxygen plasma processing according to the present invention. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-509997 A7 _B7___ V. Invention Explanation (9) of the model section. Figure 2 (Please read the precautions on the back before filling in this page) (A) Scanning electron microscope (SEM) photography of a cross section of a porous SiO: film obtained in accordance with conventional techniques; (B) A scanning electron microscope (SEM) photograph of a cross section of the obtained porous Si02 film. Fig. 3 is an FT-IR spectrum of a porous film obtained according to the present invention. [The best form for implementing the invention] According to the method for producing a porous SOG film according to the first invention, an organic silane liquid containing an organic silane, water, and alcohol is used, and a surfactant is added to make the organic silane The liquid obtained by performing acid hydrolysis or alkaline hydrolysis is coated on a semiconductor substrate, heated in the presence of a surfactant, and evaporated water, alcohols, and surfactants, and also contains other organic substances equal to the reaction In the case of a system, a porous Si02 film is produced by removing this substance. As the surfactant evaporates, a large number of void portions (void ratio: about 60% or more) are generated in the film, and a porous film is obtained. As for the raw material silane, which is printed by the employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, if it is a decomposable organosiloxane as described above, there is no particular restriction on its use. In the case of alcohols, as long as they are alcohol-based solvents such as ethanol and isopropanol, they are not particularly limited for use. Hydrolysis is decomposed with an acid, or it can be hydrolyzed with an alkali. In order to hydrolyze, an inorganic acid such as nitric acid or hydrochloric acid, an organic acid such as formic acid, or an alkali such as ammonia can be used. As the surfactant, it is preferable to use a halogenated alkyltrimethylammonium-based cationic surfactant as described above. For other surfactants, it can also be used. For example, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 509997 A7 B7 V. Description of the invention (10) (Please read the precautions on the back before filling (This page) Dimethyldecylphenylammonium chloride, Diethyldodecylphenylammonium chloride, Trimethyldodecylammonium bromide, Allyldibutyldodecyl bromide Ammonium, diethyl propyl copper based twelve yuan, etc. The amount of raw materials used is as described above. Compared with 1 mole of the organic silane, 8 to 15 moles for water, 0.5 to 1.5 moles for acid or alkali, and 0.1 to 0.4 moles for surfactant. . By appropriately selecting the amount of the surfactant used and the heat treatment conditions, a porous SiCh film having a desired specific permittivity can be selectively produced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the organic silane liquid obtained as described above is applied on a semiconductor substrate by a conventional coating method such as a spin coating method, followed by heat treatment and evaporation using a recognized infrared heating furnace and the like Water-alcohol solvents and other organic substances such as surfactants are used to produce porous Si02 films. The heat treatment conditions in this case are not particularly limited as long as the solvent, the surfactant, and the like can be evaporated to obtain a porous membrane. In order to obtain a porous film with a lower dielectric constant, the solvent is first treated and evaporated in the air at a temperature in the range of 200 to 3 50 ° C, and secondly, the surfactant can be evaporated in a vacuum in the range of 100 to 10-5 Pa, for example. The temperature of other organic substances (for example, 250 ~ 500 ° C, preferably 350 ~ 440 ° C, especially 3 80 ~ 4 50 QC), the treatment will not destroy the time of the obtained porous membrane structure Better. With respect to the obtained porous Si02 film, an electrode of an aluminum electrode was vapor-deposited and the specific permittivity was measured, and it was found that a porous SOG film was obtained in accordance with the purpose of the present invention. In other words, an interlayer insulating film having a lower specific permittivity and a substantially lower specific permittivity even when a thin film is laminated thereon in a semiconductor process after the formation of the SOG model is obtained. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ -13- 509997 A 7 B7 V. Description of the invention (11) As mentioned above, it is better to use organic silanes such as TEOS, TMOS, etc., and An interlayer insulating film having a low dielectric constant of, for example, a porosity of 60% or more is produced. (Please read the precautions on the back before filling in this page.) As the porosity becomes higher, for example, it is in the range of 80%, the influence of the specific permittivity based on the physical properties of the insulating film material is reduced. Dominated, and an interlayer insulating film with a low specific dielectric constant is obtained. From these viewpoints, a hydrolyzable alkoxide may be used instead of an organic silane. In the same case as an organic silane, a porous film can be produced as an interlayer insulating film with a low specific dielectric constant. For these oxides, alkoxides such as Ti (〇C3H7) 4, Zr (〇C4H9) 4 and other alkoxides belonging to Group 4A of the periodic table are used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾) According to the implementation form of the second method of making a porous SOG film, repeat the above steps (first step) to obtain the porous SiO2 film at least once, and A porous Si02 film is further formed on the porous Si02 film obtained in the first step. As the surfactant evaporates, a large number of void portions (void ratio: about 60% or more) are generated in the film, so that a porous film is obtained. In addition, the porous film is formed into a multilayer film to suppress the invasion of moisture. Improve hygroscopicity. In this case, if the insulating film laminated on the porous film becomes too thick, there is a problem that the so-called semi-conductor system technology, which advances in the direction of becoming thinner, tends to occur. Therefore, it is preferable to make the film thickness as thin as possible while suppressing the hygroscopicity. Although the first step is repeated a plurality of times, in this case, it is necessary to set a thinner porous film thickness compared to each of the porous film thicknesses composed of the single layer in the case of the first invention. For example, in the case of a two-layer porous film, it is preferable to set the film thickness of each porous film to a range of 0.5 # m. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -14- 509997 A7 ___B7 V. Description of the invention (12) (Please read the precautions on the back before filling this page) Raw materials Silane, alcohols, In terms of the hydrolyzed acid and base, and the surfactant, the same ones as the first invention can be used. The amount of the raw material used is preferably within the above range. The amount of the surfactant and the amount of the surfactant should be appropriately selected. The heat treatment conditions can selectively form a multilayer film of a Si02 film having a desired specific permittivity. The organic silane liquid obtained as described above is coated on a semiconductor substrate by a common spin coating method. , Repeat the process of making the porous Si02 film treated as above at least once to form a porous film. The heat treatment conditions in this case are as described above. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints these The porous SiCh film was tested for moisture absorption from the following film sides. The porous SiO2 film formed on the Si substrate was coated with a polyimide film. On the side. Cut off the four sides of the sample of one of the two samples coated with polyimide, and make the cross-section of the porous Si0 2 film appear. In the original coated state, and to target the appearance of porous Si 0 2 A moisture absorption test was performed under the same conditions as the cross section of the film, and the specific permittivity after the comparison test was used to observe whether there was moisture absorption from the side of the porous Si0 2 film. This result is considered to be based on polyimide The specific permittivity of the coated original sample after the moisture absorption test was not different from that of the sample where the side surface was cut out and a section of the porous Si0 2 film appeared. It is understood that there is no hole exit on the side of the porous Si 0 2 film, and The pores of the porous SiO2 film are aligned vertically to the substrate. According to another embodiment of the second invention, a film is formed on the porous film obtained in the first step by CVD or sputtering, for example. Either a hydrophobic SiO2 film, SiN film, or SiO * Ny film with a thickness of 100 nm or less, and cover the surface of the porous film. The film thickness of the cover layer is too thick. (CNS) A4 specification (210X297 mm) -15- 509997 A7 ______ B7 V. Description of the invention (13) (Please read the precautions on the back before filling in this page) As the total film thickness of the covered insulating film is easy to thicken, there is a so-called semiconductor that goes in the direction of thinning Process technology trends. Therefore, it is better to consider the thickness of the film that can suppress hygroscopicity and to make it as thin as possible. The cover layer can be a single layer or a plurality of layers. Second, if desired, the first In one step, a porous film is further formed on the cover layer, and the first step and the cover layer forming step described above can also be repeated multiple times. In this case, as in the case of the first embodiment described above, It is necessary to set a thinner porous film thickness compared to each of the porous film film thickness and the cover film thickness in the case of the above-mentioned first invention. For example, in the case of a two-layer porous film and a two-layer cover film, it is preferable to set each porous film in a range of 0.5 ν m and each cover layer in a range of 50 nm. 'Covering these porous membranes with a specific hydrophobic membrane can suppress the intrusion of moisture. As the raw materials, silanes, alcohols, acids and bases for hydrolysis, and surfactants, the same can be used. The amount of the raw material used is preferably within the above range. By properly selecting the amount of the surfactant used and the conditions of the heat treatment, a hydrophobic Si02 film having a desired specific permittivity can be selectively produced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The organic silane solution obtained as described above was applied on a semiconductor substrate by a conventional spin coating method, and a porous SiCh film treated as described above was produced. The heat treatment conditions in this case are as described above. In the same manner as described above, the obtained porous Si02 film 'was subjected to a confirmation test for the hygroscopicity from the side of the film as follows. The result is that there is no difference in the specific permittivity after the moisture absorption test of the original sample covered with polyimide and the sample with the porous SiO2 film cut off at the side, and this paper is applicable to China. Standard (CNS) A4 specification (210X 297 mm) -16- 509997 A7 _______B7_ V. Description of the invention (14) 'I understand that there is no hole exit on the side of the porous SiCh film, and the holes of the porous SiO2 film are vertical Aligned to the substrate. (Please read the precautions on the back before filling in this page.) For the porous 3202 film obtained in accordance with the second invention, the electrodes such as the aluminum electrode are vapor-deposited, and the specific permittivity is measured to understand that a porous material that meets the purpose of the present invention is obtained. SOG film. That is, a porous SOG film having no water intrusion into the porous film, improved hygroscopicity, and lower specific permittivity was obtained. In addition, for the porous SOG film after the hydrophobization treatment, in the semiconductor process, even if other films are laminated thereon by CVD method, there is generally no interlayer in which the specific permittivity of the porous SiO2 film is increased. Insulation film. According to the second invention, it is preferable to use an organic silane such as TEOS, TMOS, or the like. As in the first case, an interlayer insulating film having a low specific permittivity having a high porosity can be formed. Instead of the organosilane, the same silane oxide as in the first invention may be used. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ According to the third embodiment of the method for producing a porous SOG film, a porous Si0 2 film as described above was obtained, followed by an oxygen plasma treatment and an electron beam irradiation treatment Either or any of the ultraviolet irradiation treatments is performed to remove unreacted OH groups remaining in the obtained porous SiCh film. As the surfactant evaporates, a large number of void portions (void ratio: about 50% or more) are generated in the film. Thus, a porous film is obtained, and the above-mentioned hydrophobic treatment is performed on the porous film to remove residual OH groups. , Can suppress the adsorption of moisture in the atmosphere, and obtain a hydrophobic porous S ◦ G film after surface modification. As the raw materials, silanes, alcohols, acids and bases for hydrolysis, and surfactants, the same ones as the first invention can be used. The amount of the raw materials used is preferably within the above range. Appropriate selection of surfactants This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -17- 509997 A7 B7 V. Usage of the invention (15) and heat treatment (firing treatment) conditions , A hydrophobic porous Si02 film having a desired specific dielectric constant can be suitably produced. (Please read the precautions on the back before filling this page) Apply the organic silane solution obtained above to the semiconductor substrate by the usual spin coating method, and make the porous SiO: film treated as above . The heat treatment conditions in this case are as described above. In the porous SiO2 film obtained as described above, in the same manner as in the case of the second invention, a confirmation test for the moisture absorption from the side of the film was performed. The result is that the specific permittivity after the moisture absorption test of the original sample covered with polyimide was not different from that of the sample where the side surface was cut out and the cross section of the porous Si02 film appeared. It is understood that porous Si 〇2 The holes of the film are vertically aligned on the substrate. ○ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Secondly, the porous SiCh film is subjected to oxygen plasma treatment, electron beam irradiation treatment or ultraviolet irradiation treatment, and the porous film is hydrophobicized. . The reaction that occurs at this time is accompanied by dehydration. Under normal circumstances, the porous film will shrink. Although the film may be cracked, the porous film obtained by the present invention has a porosity of 50% or more. Since the thin film structure itself absorbs the generation of stress due to the above-mentioned reaction, no phenomenon such as film cracks was observed. Regarding the hydrophobizing treatment, an oxygen plasma treatment will be described below as a representative example. The oxygen plasma treatment is carried out by using an ordinary oxygen plasma treatment apparatus for microwave discharge. That is, as shown in Fig. 1, a substrate holder 3 for loading a substrate 2 to be processed is provided in the processing chamber 1, and the holder includes heating means 4 such as a heater. In addition, the side wall of the processing chamber 1 is provided with a reactive gas introduction part constituted by a discharge tube 5. The paper is connected to a microwave power source 6 and the paper size is in accordance with China National Standard (CNS) A4 (210X 297 mm) ) -18- 509997 A7 _______ B7______ 5. Description of the invention (16) Oxygen plasma generating device 8 of the plasma generating part 7. The oxygen plasma generating device 8 uses a microwave power source 6 to generate reactive gas from the oxygen introduced from the gas source 9 or a gas mixed with a small amount of other gases (for example, Ar, Kr, Xe, etc.). The slurry is configured to be introduced into the processing chamber 1. The above-mentioned processing chamber 1 is vacuum-evacuated by a vacuum pump 10 through a vacuum exhaust port 11 provided on a side wall of the processing chamber, and is then mounted on a substrate holder 3 for porous Si formed on a heated substrate 2 to be processed. Oxygen plasma treatment was performed on two membranes, and residual oH groups were removed according to the above reaction formula. That is, the residual OH group becomes H0 2 and is vaporized and exhausted from the vacuum exhaust port 11 by a vacuum pump 10. This oxygen plasma treatment is obtained, for example, by performing a predetermined time with an oxygen-containing gas flow rate of 100 to 2000 SCCM, RF and microwave power of 300 to 3000 W, and a pressure of 0.5 to 2 Torn. Although the above-mentioned plasma generating device is a downstream type, a plasma generating device such as a parallel plate electrode type or an ECR type may be used. There are no particular restrictions on the means of igniting plasma. Furthermore, in addition to the above-mentioned oxygen plasma treatment, a treatment method capable of removing the remaining fluorene groups of the porous film may be used. For example, with respect to a porous film, an electron beam can be irradiated with an electron beam or ultraviolet rays can be removed by a conventional method. With respect to the obtained porous SOG film, an electrode such as an aluminum electrode was vapor-deposited, and the specific permittivity was measured, and it was found that a porous SOG film meeting the purpose of the present invention was obtained. That is, a porous interlayer insulating film having no moisture absorption and a lower specific permittivity is obtained, that is, in a semiconductor process after the hydrophobization process, even if a thin film is laminated thereon, there is generally an interlayer which has a substantially higher dielectric constant. Insulation film. As mentioned above, it is better to use organic silanes such as TEOS or TMOS. As in the first case, a low specific permittivity with high porosity can be produced. This paper applies the Chinese National Standard (CNS) A4 specification (210 × 297). Mm) —------- clothing-*, (please read the precautions on the back before filling this page), -5r-m Intellectual Consumption Cooperatives, Employees Cooperative 19-509997 A7 B7 5 An interlayer insulating film of invention description (17). Instead of the organosilane, the same sand oxygen plant as the first invention may be used. According to one embodiment of the method for producing a porous SOG film according to the fourth invention, when a porous Si02 film is obtained, first, the above-mentioned heat treatment is performed at a temperature of 200 to 3 50 t in air. The atmosphere is preferably performed in a vacuum at a temperature of 3 50 to 450 ° C (preferably 380 to 450 ° C). The heat treatment atmosphere is set to these states, and at least the wall surface inside the pores of the obtained porous film is covered with a hydrophobic group, and at the same time, the specific permittivity is lowered. According to this invention, as the surfactant is evaporated, a large number of void portions (void ratio: about 50% or more) are generated in the film, so that a porous film is obtained. In the heat treatment step of hole formation, the hole formation (ie, the formation of a porous film) is ended with the hydrophilicity of the surfactant attached based on the state of the film surface inside the hole, and the hydrophobic group of the surfactant is oriented relative to the inside of the hole. The reverse surface state of the membrane surface (that is, the state from the membrane surface inside the cavity toward the cavity space direction) exists, and the wall surface inside the cavity is covered with a hydrophobic base. Therefore, since at least the wall surface inside the pores becomes hydrophobic, the adsorption of moisture in the atmosphere can be suppressed, and a surface-modified hydrophobic porous film can be obtained. As the raw materials, silane, alcohols, hydrolyzed acids and bases, and surfactants, the same ones as the first invention can be used. The amount of the raw materials used is preferably within the above range. By appropriately selecting the amount of the surfactant used and the conditions of the heat treatment (firing treatment), a hydrophobic porous SiCh film having a desired specific permittivity can be suitably produced. Apply the organic silane liquid obtained as above to the standard of the spin-coating method. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). ----------- 礞 Μ (Please read the back first Please pay attention to this page and fill in this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives-20- 509997 A7 B7 V. Invention Description (18) (Please read the notes on the back before filling this page) On the semiconductor substrate, a porous Si0 2 film processed as described above was fabricated. The heat treatment conditions in this case are preferably those under the above-mentioned temperature conditions. That is, in order to obtain a hydrophobic porous film having a lower specific dielectric than that, first, it is treated in the air at a temperature ranging from 200 to 3 50 ° C, and a water-alcohol-based solvent is evaporated, and secondly, under nitrogen. In a gas atmosphere with a low absolute dielectric constant, etc., in a vacuum of 100 to 1 (T5Pa range is preferred, and other organic substances that can evaporate the surfactant, etc.), the porous membrane structure obtained is not damaged. Treatment of time. The porous SiO2 film thus obtained was subjected to a confirmation test for the hygroscopicity from the side of the film in the same manner as in the case of the second invention. The specific permittivity after the moisture absorption test of the original sample coated with amine and that of the sample with the porous ^ 〇2 film cut off at the side. There is no difference. Knowing the pores of the porous Si〇2 film, it is aligned vertically to Substrate: The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed electrodes for the porous film obtained in accordance with the fourth invention, vapor-deposited aluminum electrodes, etc., and measured the specific permittivity to understand that a hydrophobic porous SOG film that meets the purpose of the present invention is obtained. . ·· Porous interlayer insulation film with no moisture absorption and lower specific permittivity, that is, in the semiconductor process after the hydrophobization treatment, even if a thin film is further laminated on the interlayer insulation, there is generally no interlayer insulation with an increase in specific permittivity. As described above, it is preferable to use an organic silane such as TEOS, TMOS, or the like. In the same manner as in the first case, an interlayer insulating film having a high specific porosity and a low specific dielectric can be produced. The first invention can also be used. The same siloxane is used instead of the organosilane. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -21-509997 A7 _______B7 V. Description of the invention (19) For the above-mentioned porous material obtained by the present invention There is no absorption peak of 〇Η group when the spectrum is measured by FT-iR analysis. (Please read the precautions on the back before filling in this page.) Residue of the porous film obtained by the above 1st to 4th inventions For the unreacted hydrophilic OH radical, if the porous membrane is subjected to an oxygen plasma treatment using a conventional polishing device or an electron beam irradiation treatment recognized by an electron beam gun or The ultraviolet irradiation treatment can remove the residual OH group to further improve the hydrophobicity of the porous body. [Example] Hereinafter, an example of the present invention will be described with reference to the drawings. (Example 1: First invention) Intellectual Property Bureau, Ministry of Economic Affairs Employee Consumer Cooperative Co., Ltd. printed using 0.7 mol of nitric acid relative to TEOS 1 mol, HO: 12 mol, ethanol 15 mol, and a predetermined amount of surfactant, as a reaction solution for the preparation of porous SiOa membranes. Raw materials, and prepare a SiO2 solution of a porous SOG membrane. Add 0.1, 0.15, 0.2, and 0.25 n-hexadecyltrimethylammonium chloride (manufactured by Kanto Chemical Co., Ltd.) to TOES 1 mole. , Trade name: CTAC1) as a surfactant, and a coating liquid is prepared. Each coating solution was spin-coated on a semiconductor substrate (sample Nos. A1 to H1) at 3000 rpm. Using a recognized infrared heating furnace, as shown in Table 1, each coated substrate is initially treated at 200 to 400 ° C in air, and then 100 to 1 (T5Pa in an atmosphere of 400 to 400). ° C for firing treatment, to obtain a porous film of 0. In this case, the time from the initial processing temperature of 200 ° C to the next step of the processing temperature of 400 ° C is 60 minutes. China National Standard (CNS) A4 specification (210X297 mm) -22- 509997
7 7 A R 五、發明説明（20 ) (請先閲讀背面之注意事項再填寫本頁) 況之升溫速度亦相同。該升溫速度雖未說有特別之限制， 但是對於得之薄膜的薄膜材質，以薄膜波紋少、漏電値亦 小之範圍爲佳。又’真空燒成中之維持時間係以不產生薄 膜構造之破壞的範圍爲佳，於本實施例中係維持3 0分鐘來 .燒成。 針對該等所得之多孔質31〇2膜，蒸鍍鋁電極後，使用 HP公司製tfc介電率卞則定裝置（re IMPEDANCE ANALYZER 4 1 9 1 A ) ’於1週時間後測定比介電率。所得之比介電率示 於第1表。 (第1表） 試樣 編號 最初之加 熱處理 (°C ) 下一個步驟之 加熱處理 (°C ) 界面活性劑 /TEOS (莫耳比） 比介電率 { 8 ! ε 〇) A1 200 400 0.1 3.8 B1 200 400 0.15 3.2 C1 200 400 0.2 2.0 D1 200 400 0.25 1.5 E1 250 400 0.25 1.5 F1 300 400 0.25 2.5 G1 350 400 0.25 3.2 H1 400 400 0.25 4.1 經濟部智慧財產局5貝工消費合作社印製 如第1表所知，於空氣中以200〜350 °C處理，其次於真 空中以400 °C處理的情況下，得到具有1.0〜4.0範圍內之低 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 23- 509997 A7 ____B7_ 五、發明説明（21 ) (請先閲讀背面之注意事項再填寫本頁) 比介電率之S〇G膜。又，所得之SOG膜，於半導體製程中 ，即使以CVD等進一步於其上層合其他薄膜的情況下，大 體上亦無比介電率上升。 針對依照上述實施例於基板上製造多孔質SOG膜的情 況，以及以傳統技術（以無機SOG之矽烷化的方法）於基 板上製造多孔質〗1〇2膜的情況，以掃描型電子顯微鏡（ SEM )攝影該剖面相片，並觀測各多孔質膜之薄膜性質狀 態。由該SEM相片，於傳統薄膜的情況，觀測到大直徑之 孔洞（數nm〜數十nm)(第2圖（A))，而於本發明之SOG 膜則爲極小之孔洞，實際上了解爲不能以SEM觀測之lnm 以下之孔洞（第2圖（B))。 ’ 又，在使用氯化月桂基三甲基銨（花王（株）製，商 品名：寇達明24P )取代氯化正十六烷基三甲基銨來作爲 界面活性劑的情況下，亦得到與上述相同之結果。 (實施例2 :第2發明） 經濟部智慧財產局員工消费合作社印製 於依照實施例1·記載之成膜方法而得之多孔質膜（試 樣編號A2〜H2，膜厚：0.5 M m )之表面上，重複該成膜步 驟，層合同樣之多孔質Sl〇2膜（膜厚：〇.5 V m )，形成由 雙層多孔質膜所構成之絕緣膜。 針對該等所得之多層的多孔質31〇2膜，蒸鍍鋁電極後 ，使用HP公司製比介電率測定裝置（RE IMPEDANCE ANALYZER 4191 A )，於1週時間後測定比介電率。所得之 比介電率示於第2表。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 509997 Α7 Β7 五、發明説明（22 ) (第2表） 試樣 編5虎 最初之加 熱處理 (°C ) 下一個步驟 之加熱處理 (V ) 界面活性劑 /TEOS (莫耳比） 比介電率 (<S / 6 〇) Α2 200 400 0.1 2.9 Β2 200 400 0.15 2.5 C2 200 400 0.2 1.9 D2 200 400 0.25 1.5 Ε2 250 400 0.25 1.8 F2 300 400 0.25 2.3 G2 350 400 ，0.25 2.8 Η2 400 400 0.25 3.4 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如第2表所知，於空氣中以200〜3 5 0 °C處理，其次於真 空中以400 °C處理的情況下，得到具有1.5〜2.9範圍內之低 比介電率之SOG膜。又，所得之S〇G膜，於半導體製程中 ，即使以CVD等進一步於其上層合其他薄膜的情況下，大 體上亦無比介電率上升。又，無強度上之任何問題，與其 單層的情況，在相同膜厚的情況，強度上亦提昇。 針對依照上述實施例於基板上製造由單層構成之多孔 質SOG膜的情況，以及以傳統技術（以無機SOG之矽烷化 的方法）於基板上製造多孔質Si〇2膜的情況，以掃描型電 子顯微鏡（S E Μ )攝影該剖面相片，並觀測各多孔質膜之 薄膜性質狀態。由該SEM相片，與實施例1之情況相同地 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -25- A 7 ____ _ _B7_ 五、發明説明（23 ) (請先閲讀背面之注意事項再填寫本頁) ’於傳統薄膜的情況，觀測到大直徑之孔洞（數nm〜數十 nm )，而於本發明之SOG膜則爲極小之孔洞，實際上了解 爲不能以SEM觀測之lnm以下之孔洞。以SEM來觀測本實 施例情況之僅由單層所構成之薄膜，明瞭多層膜多層膜的 情況亦顯示同樣的傾向。 又，在使用氯化月桂基三甲基銨（花王（株）製，商 品名：寇達明24P )取代氯化正十六烷基三甲基銨來作爲 界面活性劑的情況下，亦得到與上述相同之結果。 (實施例3 :第2發明） 於以實施例2之第一步驟所得之多孔質31〇2膜（膜厚 :0.5 // m )之表面上，以CVD法或濺鍍法，形成Si〇2膜 、SiNx膜或Si〇xNy膜（膜厚：50nm )，並覆蓋該多孔質膜 之表面。其次，以相同條件來重複該第一步驟及覆蓋步驟 ，於該覆蓋層上依序形成再一層多孔質膜及覆蓋層。 經濟部智慧財產局工消费合作社印¾ 針對該等所得之多層的多孔質膜，蒸鍍鋁電極後，使 用HP公司製比介電率測定裝置（RE IMPEDANCE ANALYZER 4191 A )來測定比介電率時，由於得到與第2表 之比介電率相同的値，該等多層之多孔質膜亦爲有用之層 間絕緣膜。 (實施例4 :第2發明） 依照實施例1記載之成膜方法所得之多孔質^〇2膜（ 試樣編號A3〜H3，膜厚：0.5 // m )之表面上，以CVD法 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） " ' -26- 509997 A7 _ B7_ _ 五、發明説明（24 ) 或濺鍍法，形成Si〇2膜、SiNx膜或SiCLNy膜（膜厚：50nm )，並覆蓋該多孔質膜之表面。 (請先閲讀背面之注意事項再填寫本頁) 針對該等所得之疏水性多孔質Si〇2膜，蒸鍍鋁電極後 ，使用HP公司製比介電率測定裝置（RE IMPEDANCE ANALYZER 4191 A )，於1週時間後來測定比介電率。所得 之比介電率示於第3表。 (第3表） 試樣 編號 最初之加 熱處理 (°C ) 下一個步驟 之加熱處理 (°C ) 界面活性劑 /TEOS (莫耳比） 比介電率 A (ε/e 〇) 比介電率 B (£ /£ 〇 ) A3 200 400 0.1 3.8 4.0 B3 200 400 0.15 3.2 3.4 C3 200 400 0.2 2.0 2.3 D3 200 400 0.25 1.5 1.7 E3 250 400 0.25 1.5 1.8 F3 300 400 0.25 2.5 2.7 G3 350 400 0.25 3.2 3.4 H3 400 400 0.25 4.1 4.4 經濟部智慧財產局員工消費合作社印製 第3表中，比介電率A係於形成多孔質膜後，針對蒸 鍍未覆蓋疏水性膜之鋁電極的試樣，於放置室內1週時間 後所測定者，又，針對蒸鍍覆蓋有疏水性膜之鋁電極的試 樣，於放置室內1週時間後所測定者。 如第3表所知，於空氣中以200〜3 50 °C處理，其次於真 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27- 509997 A7 B7 五、發明説明（25 ) (請先閲讀背面之注意事項再填寫本頁) 空中以400 °C處理的情況下，得到具有1.0〜4.0範圍內之低 比介電率A之SOG膜，且，比介電率B大致上亦無變化。 再者，所得之疏水性多孔質SOG膜，於半導體製程中，即 使以CVD等進一步於其上層合其他薄膜的情況下，大體上 亦無比介電率上升。 針對依照上述實施例於基板上製造多孔質SOG膜的情 況，以及以傳統技術（以無機SOG之矽烷化的方法）於基 板上製造多孔質SiCh膜的情況，以掃描型電子顯微鏡（ SEM )攝影該剖面相片，並觀測各多孔質膜之薄膜性質狀 態。由該SEM相片，與實施例1之情況相同地，於傳統薄 月旲的情況’觀測到大直徑之孔洞（數nm〜數十nm )，而於 本發明之SOG膜則爲極小之孔洞，實際上了解爲不能以 SEM觀測之lnm以下之孔洞。 又，在使用氯化月桂基三甲基銨（花王（株）製，商 品名：寇達明24P )取代氯化正十六烷基三甲基銨來作爲 界面活性劑的情況下，亦得到與上述柑同之結果。 經濟部智慧財產局員工消f合作社印災 (實施例5 :第3發明） 以利用通常之微波放電的氧電漿處理裝置來處理依照 實施例1記載之成膜方法所得之多孔質Si〇2膜（試樣編號 A4〜H4，膜厚：0·7 μ m，空隙率：80 °/〇 )。即，在設置 於示於第1圖之氧電漿處理室1內之基板夾具3上，裝載製 作多孔質膜之被處理基板2，同時以加熱器4來加熱（1 〇〇 °C )。另外，在設置於該處理室1之側壁的氧電漿產生裝 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -28 509997 A7 B7 五、發明説明（26 ) (請先閱讀背面之注意事項再填寫本育) 置8上，經由連接於由放電管所構成之反應性氣體導入部 分5的氣體源9，導入氧氣100SCCM，導入連接於電漿產 生部分7之微波電源6 ( 2.45 GHz )並使該氧氣電漿化。導 入該電漿於該處理室1內之被處理基板2上，進行1〜5分鐘 範圍之氧電漿處理。該處理室之壓力爲0.1 Tori·。將反應結 果所得之H〇2氣化，並以真空泵10從真空排氣口 11排氣。 以FT-IR分析來對於如上述氧電漿處理之多孔質膜來測 定光譜（第3圖）。如由第3圖所知，與無氧電漿處理之多 孔質膜的情況不同，以本實施例之氧電漿處理之多孔質膜 的情況，無3400(:1^1附近之〇H基之吸收峰，了解已除去殘 留〇H基。 個別針對該等所得之疏水性多孔質Si〇2膜及對照之多 孔質31〇2膜，蒸鍍鋁電極'後，使用HP公司製比介電率測定 裝置（RE IMPEDANCE ANALYZER 4191 A )來 t則定比介電 率。所得之比介電率示於第4表。 經濟部智慧財產局員工消费合作社印製 第4表中，比介電率A係針對形成多孔質膜後未進行 氧電漿處理地，蒸鍍鋁電極之對照試樣，放置室內1週後 之所測定者；又，比介電率B係針對在形成多孔質膜後進 行氧電獎處理之疏水化多孔質膜上蒸鑛銘電極之試樣，放 置室內1週後之所測定者。 ^紙張尺度適用中國國家揉準(CNS ) A4規格（210X297公釐） -29- 509997 五、發明説明（27) (第4表） 試樣編 號 最初之加 熱處理 (°C ) 下一個步驟 之加熱處理 (°C ) 界面活性劑 /TEOS (莫耳比） 比介電率 A (ε / ε 〇) 比介電率 Β (β / <£ 〇 ) A4 200 400 0.1 8.2 3.8 B4 200 400 0.15 8.5 3.2 C4 200 400 0.2 7.6 2.0 D4 200 400 0.25 7.5 1.5 E4 250 400 0.2 5 7.2 1.5 F4 300 400 0.25 8.1 2.5 G4 350 400 0.25 8.3 3.2 H4 400 400 0.25 - 10.2 4.1 · (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如第4表所知，於空氣中以200〜350 °C處理，其次於真 空中以400 °C處理的情況下，放置室內1週時間，則變爲具 有7.2〜8.5範圍內之高比介電率（比介電率A)，而氧電漿 處理所得之疏水化多孔質的情況，亦放置室內1週時間， 具有1 · 5〜3 · 8範圍之低比介電率（比介電率B )。因此，測 定比介電率B者較比介電率A爲低値時，表示除去殘留〇H 基，並無水分吸附的意思。再者，氧電漿處理之疏水性多 孔質SOG膜，於半導體製程中，即使以CVD等進一步於其 上層合其他薄膜的情況下，大體上亦無比介電率上升。 針對依照上述實施例於基板上製造多孔質SOG膜的情 況（未進行氧電漿處理），以及以傳統技術（以無機S〇G 之矽烷化的方法）於基板上製造多孔質Si〇2膜的情況，以 -30- 509997 A7 _B7 _ 五、發明説明（28 ) (請先閱讀背面之注意事項再填寫本頁) 掃描型電子顯微鏡（SEM )攝影該剖面相片，並觀測各多 孔質膜之薄膜性質狀態。由該SEM相片，與實施例1之情 況相同地，於傳統薄膜的情況，觀測到大直徑之孔洞（數 nm〜數十nm )，而於本發明之SOG膜則爲極小之孔洞，實 際上了解爲不能以SEM觀測之lnm以下之孔洞。 又，在使用氯化月桂基三甲基銨（花王（株）製，商 品名：寇達明24P )取代氯化正十六烷基三甲基銨來作爲 界面活性劑的情況下，亦得到與上述相同之結果。 (實施例6 :第4發明） 經濟部智慧財產局員工消費合作社印製 使用相對於TEOS 1莫耳之硝酸’0.7莫耳、H〇2 12莫耳 、乙醇1 5莫耳、既定量之界面活性劑，作爲調製用於多孔 質Si〇2膜製作之反應液的原料，並調製多孔質S〇G膜之 Si〇2液。添加相對於TOES 1莫耳之0.1、0.15、0.2、0.25 之氯化正十六烷基三甲基銨（關東化學（株）製，商品名 :CTAC 1 )作爲界面活性劑，並調製塗佈液。於半導體基 板（試料編號A1〜Η 1·)上，以3000轉/分鐘之條件旋轉塗佈 各塗佈液。使用公認之紅外線加熱爐，如於第5表來表示 所塗佈之各基板，於空氣中200〜400 °C來進行第一加熱處理 步驟，其次於100〜l(T5Pa之氛圍氣體中400 °C來進行第二加 熱處理（燒成處理）步驟，得到疏水性之多孔質Si〇2膜（ 試樣編號A5〜H5)。又，如第6表所示，接著上述第一步 驟之後，於100〜10_5Pa之氛圍氣體中3 50 °C、400 °C、450 °C、500 °C來進行第二加熱處理步驟，得到疏水性之多孔 本紙張又度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - 509997 Α7 Β7 五、發明説明（29 ) 質SiCh膜（試樣編號15〜L5 )。 從最初之處理溫度200 °C升溫至下一步驟之處理溫度 400 °C之時間爲60分鐘，其他情況之升溫速度亦相同。該 升溫速度雖未說有特別之限制，但對於得之薄膜的薄膜材 質，以薄膜波紋少、漏電値亦小之範圍爲佳。又，真空燒 成中之維持時間係以不產生薄膜構造之破壞的範圍爲佳， 於本實施例中係維持30分鐘來燒成。 以FT-IR分析來對於如上述所得之多孔質膜來測定光譜 時，與第3圖之情況相同地，無3400cm·1附近之〇H基之吸 收峰。 針對該等所得之疏水性多孔質Si〇2膜（試樣編號 A5〜L5 )，蒸鍍鋁電極後，使用HP公司製比介電率測定裝 置（RE IMPEDANCE ANALYZER 4191A ) ’於 ί 週時間後 測定比介電率。所得之比介電率示於第5表及第6 « ° (請先閲讀背面之注意事項再填寫本頁) I裝- 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -32- 509997 A7 B7 五、發明説明（3〇 ) (第5表） 試樣編號 最初之加熱 處理（°C ) 下一個步驟 之加熱處理 CC ) 界面活性劑 /TEOS (莫耳比） 比介電率 (ε / £ 〇) A5 200 400 0.1 3.8 B5 200 400 0.15 3.2 C5 200 400 0.2 2.0 D5 200 400 0.25 1.5 E5 250 400 0,25 1.5 F5 300 400 0.25 2.5 G5 350 400 0.25 3.2 H5 400 400 ，0.25 4.1 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消f合作社印製 如第5表所知，於空氣中以200〜350 °C處理，其次於真 空中以400 °C處理的情況下，得到具有1.0〜4.0範圍內之低 比介電率之SOG膜。又’所得之SOG膜，於半導體製程中 ，即使以CVD等進一步於其上層合其他薄膜的情況下，大 體上亦無比介電率上升。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -.Ί 509997 A7 B7 五、發明説明（31 ) (第6表） 試樣編號 最初之加熱 處理（°C ) 下一個步驟 之加熱處理 (°C ) 界面活性劑 /TE0S (莫耳比） 比介電率 (£/£〇) 15 200 350 0.25 2.8 J5 250 400 0.25 1.7 K5 300 450 0.25 2.2 L5 350 5 00 0.25 3.0 (請先閱讀背面之注意事項再填寫本頁) 如第5表所知，了解於空氣中以200〜350 °C處理，其次 於真空中以350〜450 °C處理的情況下，得到具有4.0以下之 低比介電率之SOG膜。 ’ 如由FT-IR光譜所得知，無〇H基光譜，即表示爲所謂 無起因於OH基之水分吸收，所謂不會腐蝕A1等之配線的 意思。再者，氧電漿處理之疏水性多孔質SOG膜，於半導 體製程中，即使以CVD等進一步於其上層合其他薄膜的情 況下，大體上亦無比介電率上升。 經濟部智慧財產局員工消費合作社印製 針對依照本實施例於基板上製造多孔質SOG膜的情況 (試樣編號〗5 )，以及以傳統技術（以無機SOG之矽烷化 的方法）於基板上製造多孔質Si〇2膜的情況，以掃描型電 子顯微鏡（SEM )攝影該剖面相片，並觀測各多孔質膜之 薄膜性質狀態。由該SEM相片，與實施例1之情況相同地 ，於傳統薄膜的情況，觀測到大直徑之孔洞（數n m〜數十 nm )，而於本發明之SOG膜則爲極小之孔洞，實際上了解 爲不能以SEM觀測之lnm以下之孔洞。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34- 509997 A7 B7 五、發明説明（32 ) 又’在使用氯化月桂基三甲基銨（花王（株）製，商 品名：寇達明24P)取代氯化正十六院基三甲基錢來作爲 界面活性劑的情況下，亦得到與上述相同之結果。 .【產業上之利用可能性】 如以上，關於本發明之多孔質SOG膜之製作方法，係 有用於形成在LSI等之半導體製程之領域的層間絕緣膜時。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -35-7 7 A R V. Description of the invention (20) (Please read the precautions on the back before filling in this page) The heating rate is the same. Although this temperature increase rate is not particularly limited, it is preferable that the film material of the obtained film has a range of less film ripples and less leakage current. The maintenance time during the vacuum firing is preferably in a range that does not cause damage to the thin film structure. In the present embodiment, the firing is maintained for 30 minutes. For the obtained porous 3202 film, an aluminum electrode was vapor-deposited, and then a tfc dielectric constant setting device (re IMPEDANCE ANALYZER 4 1 9 1 A) manufactured by HP was used to measure the specific permittivity after one week. . The obtained specific permittivity is shown in Table 1. (Table 1) Sample number Initial heat treatment (° C) Next heat treatment (° C) Surfactant / TEOS (Molar ratio) Specific permittivity {8! Ε 〇) A1 200 400 0.1 3.8 B1 200 400 0.15 3.2 C1 200 400 0.2 2.0 D1 200 400 0.25 1.5 E1 250 400 0.25 1.5 F1 300 400 0.25 2.5 G1 350 400 0.25 3.2 H1 400 400 0.25 4.1 Intellectual Property Bureau of the Ministry of Economy 5 Known in Table 1, when treated at 200 ~ 350 ° C in air, followed by 400 ° C in vacuum, a low paper size in the range of 1.0 ~ 4.0 is obtained. The Chinese National Standard (CNS) A4 specification is applicable. (210X297 mm) 23- 509997 A7 ____B7_ V. Description of the invention (21) (Please read the precautions on the back before filling in this page) SOG film with specific permittivity. In addition, in the semiconductor manufacturing process, even when other thin films are further laminated thereon by CVD or the like, the dielectric constant is generally not increased. For a case where a porous SOG film is manufactured on a substrate according to the above embodiment, and a case where a porous film is manufactured on a substrate by a conventional technique (a method of silylation of inorganic SOG), a scanning electron microscope ( SEM) photograph the cross-section photograph, and observe the thin film property state of each porous membrane. From this SEM photograph, in the case of a conventional thin film, a large-diameter hole (several nm to several tens of nm) was observed (Figure 2 (A)), while the SOG film in the present invention is an extremely small hole. Holes below 1 nm that cannot be observed by SEM (Figure 2 (B)). 'Also, in the case where lauryl trimethyl ammonium chloride (trade name: Kodaming 24P, manufactured by Kao Corporation) is used as a surfactant, it is also obtained Same result as above. (Example 2: Second invention) A porous film (sample Nos. A2 to H2, film thickness: 0.5 M m) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and produced according to the film formation method described in Example 1. ) On the surface, repeat the film forming step, and laminate the same porous S102 film (film thickness: 0.5 V m) to form an insulating film composed of a double-layer porous film. For the obtained multilayer porous 3202 film, an aluminum electrode was vapor-deposited, and then a specific permittivity measuring device (RE IMPEDANCE ANALYZER 4191 A) manufactured by HP was used to measure the specific permittivity after one week. The obtained specific permittivity is shown in Table 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -24- 509997 A7 B7 V. Description of the invention (22) (Table 2) Sample series 5 Tiger initial heat treatment (° C) Next Heat treatment of step (V) Surfactant / TEOS (Molar ratio) Specific permittivity (< S / 6 〇) Α2 200 400 0.1 2.9 Β2 200 400 0.15 2.5 C2 200 400 0.2 1.9 D2 200 400 0.25 1.5 Ε2 250 400 0.25 1.8 F2 300 400 0.25 2.3 G2 350 400, 0.25 2.8 Η 2 400 400 0.25 3.4 (Please read the precautions on the back before filling out this page) The Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs printed as Table 2 knows, The SOG film having a low specific permittivity in the range of 1.5 to 2.9 was obtained in the air at 200 to 350 ° C, followed by 400 ° C in vacuum. In addition, in the semiconductor manufacturing process, even when other thin films are further laminated thereon by CVD or the like, the dielectric constant is generally not increased. In addition, there is no problem in strength, and the strength is also improved in the case of the same film thickness as in the case of a single layer. For the case where a porous SOG film composed of a single layer is manufactured on a substrate according to the above embodiment, and the case where a porous SiO2 film is manufactured on a substrate by a conventional technique (the method of silylation of an inorganic SOG), scanning is performed. A type electron microscope (SE M) photographed the cross-section photograph, and observed the film property state of each porous membrane. From this SEM photo, the paper size is the same as the case of Example 1. The Chinese national standard (CNS) A4 specification (210X297 mm) is applied. -25- A 7 ____ _ _B7_ V. Description of the invention (23) (Please read the back first (Please note this page before filling in this page) 'In the case of traditional thin films, large diameter holes (several nm to several tens of nm) were observed, while the SOG film in the present invention has extremely small holes, and it is actually understood that the SEM cannot be used. Observe holes below lnm. Observing the thin film consisting of a single layer in the case of this embodiment by SEM, it is clear that the multilayer film and the multilayer film show the same tendency. In addition, when lauryl trimethyl ammonium chloride (trade name: Kodaming 24P, manufactured by Kao Corporation) was used as the surfactant, it was also obtained with The same result as above. (Example 3: Second invention) On the surface of the porous 3120 film (film thickness: 0.5 // m) obtained in the first step of Example 2, Si was formed by CVD method or sputtering method. 2 films, SiNx films, or SiOxNy films (film thickness: 50 nm), and cover the surface of the porous film. Next, the first step and the covering step are repeated under the same conditions, and another porous film and a covering layer are sequentially formed on the covering layer. Printed by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ For the obtained multilayer porous film, an aluminum electrode was vapor-deposited, and then the specific permittivity measurement device (RE IMPEDANCE ANALYZER 4191 A) manufactured by HP was used to measure the specific permittivity. In this case, since the same specific permittivity as that in Table 2 is obtained, these multilayer porous films are also useful interlayer insulating films. (Example 4: Second invention) On the surface of the porous ^ 〇2 film (sample number A3 ~ H3, film thickness: 0.5 // m) obtained according to the film forming method described in Example 1, the CVD method was used. Paper size applies Chinese National Standard (CNS) A4 specification (210X29 * 7mm) " '-26- 509997 A7 _ B7_ _ V. Description of the invention (24) or sputtering method to form Si〇2 film, SiNx film or A SiCLNy film (film thickness: 50 nm) covers the surface of the porous film. (Please read the precautions on the back before filling in this page.) For the obtained hydrophobic porous Si02 films, aluminum electrodes were vapor-deposited, and then a specific permittivity measuring device (RE IMPEDANCE ANALYZER 4191 A) manufactured by HP was used. The specific permittivity was measured after 1 week. The obtained specific permittivity is shown in Table 3. (Table 3) Sample number Initial heat treatment (° C) Next heat treatment (° C) Surfactant / TEOS (Molar ratio) Specific permittivity A (ε / e 〇) Specific permittivity Rate B (£ / £ 〇) A3 200 400 0.1 3.8 4.0 B3 200 400 0.15 3.2 3.4 C3 200 400 0.2 2.0 2.3 D3 200 400 0.25 1.5 1.7 E3 250 400 0.25 1.5 1.8 F3 300 400 0.25 2.5 2.7 G3 350 400 0.25 3.2 3.4 H3 400 400 0.25 4.1 4.4 In the third table printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the specific permittivity A is after the formation of a porous film, and the sample of an aluminum electrode that is not covered with a hydrophobic film is evaporated. Those who were measured after being allowed to stand in the room for one week, and those who were vapor-deposited aluminum electrodes covered with a hydrophobic film were measured after being allowed to stand in the room for one week. As known in Table 3, it is treated in the air at 200 ~ 3 50 ° C, followed by the genuine paper size which applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 509997 A7 B7 V. Description of the invention ( 25) (Please read the precautions on the back before filling in this page) When the air is treated at 400 ° C, an SOG film with a low specific permittivity A in the range of 1.0 to 4.0 is obtained, and the specific permittivity B There has been no change in general. In addition, the obtained dielectric porous SOG film has a substantially higher dielectric constant in the semiconductor manufacturing process, even when other thin films are laminated thereon by CVD or the like. For the case where a porous SOG film is manufactured on a substrate according to the above embodiment, and the case where a porous SiCh film is manufactured on a substrate by a conventional technique (the method of silylation of inorganic SOG), a scanning electron microscope (SEM) is used to photograph This section photograph, and observe the film properties of each porous membrane. From this SEM photograph, as in the case of Example 1, a large-diameter hole (several nm to several tens of nm) was observed in the case of the conventional thin moon, and the SOG film in the present invention is an extremely small hole. Actually, it is understood as a hole below 1 nm which cannot be observed by SEM. In addition, when lauryl trimethyl ammonium chloride (trade name: Kodaming 24P, manufactured by Kao Corporation) was used as the surfactant, it was also obtained with The same results as above. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Cooperative Society (Example 5: Third Invention) The porous Si obtained by the film-forming method described in Example 1 was processed by an oxygen plasma processing apparatus using a general microwave discharge. Film (Sample Nos. A4 to H4, film thickness: 0.7 μm, void ratio: 80 ° / 〇). That is, the substrate holder 3 provided in the oxygen plasma processing chamber 1 shown in FIG. 1 is loaded with a substrate 2 to be processed to make a porous membrane, and is heated by a heater 4 (100 ° C). In addition, the size of the paper produced by the oxygen plasma installed on the side wall of the processing chamber 1 applies the Chinese National Standard (CNS) A4 (210X 297 mm) -28 509997 A7 B7 V. Description of the invention (26) (please first Read the notes on the back side and fill in this education.) Place 8 on the gas source 9 connected to the reactive gas introduction part 5 composed of a discharge tube, introduce 100SCCM of oxygen, and introduce the microwave power supply 6 connected to the plasma generation part 7. (2.45 GHz) and plasma the oxygen. The plasma is introduced onto the substrate 2 to be processed in the processing chamber 1 and subjected to an oxygen plasma treatment in a range of 1 to 5 minutes. The pressure in the processing chamber was 0.1 Tori ·. The H2O2 obtained as a result of the reaction was gasified and exhausted from a vacuum exhaust port 11 by a vacuum pump 10. FT-IR analysis was used to measure the spectrum of the porous membrane treated with the above-mentioned oxygen plasma (Fig. 3). As can be seen from FIG. 3, unlike the case of a porous membrane treated with an oxygen-free plasma, the case of the porous membrane treated with an oxygen-based plasma in this example does not have a 3400 (: OH group around 1 ^ 1). The absorption peak was obtained to understand that the residual 0H group had been removed. The hydrophobic porous Si02 film and the comparative porous 3120 film obtained by these were individually vapor-deposited with an aluminum electrode, and then a specific dielectric made by HP was used. The specific permittivity is determined by a measuring device (RE IMPEDANCE ANALYZER 4191 A). The specific permittivity obtained is shown in Table 4. The specific permittivity A is printed in Table 4 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is for those who do not perform oxygen plasma treatment after the formation of the porous film. The reference sample of the aluminum electrode is vapor-deposited and measured after being placed in the room for 1 week. The specific permittivity B is for the measurement after the formation of the porous film. Samples of steam-minded electrodes on hydrophobicized porous membranes treated with the oxygen-electricity award are measured after being placed in the room for 1 week. ^ The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -29- 509997 V. Description of the invention (27) (Table 4) Initial heat treatment of sample number (° C) Heat treatment in the next step (° C) Surfactant / TEOS (Molar ratio) Specific permittivity A (ε / ε 〇) Specific permittivity B (β / < £ 〇) A4 200 400 0.1 8.2 3.8 B4 200 400 0.15 8.5 3.2 C4 200 400 0.2 7.6 2.0 D4 200 400 0.25 7.5 1.5 E4 250 400 0.2 5 7.2 1.5 F4 300 400 0.25 8.1 2.5 G4 350 400 0.25 8.3 3.2 H4 400 400 0.25-10.2 4.1 · ( Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, as known in Table 4, processed at 200 ~ 350 ° C in air, followed by 400 ° C in vacuum In the case, when placed in the room for 1 week, it will have a high specific permittivity (specific permittivity A) in the range of 7.2 to 8.5, and the case of hydrophobic porosity obtained by oxygen plasma treatment will also be placed in the room 1 It has a low specific permittivity (specific permittivity B) in the range of 1 · 5 ~ 3 · 8 in week time. Therefore, when the specific permittivity B is measured to be lower than the specific permittivity A, it means that the residue is removed. H group has no meaning of moisture adsorption. In addition, the hydrophobic porous SOG film treated by oxygen plasma is used in semiconductors. In the manufacturing process, even when other thin films are laminated on top of it by CVD, the dielectric constant is generally not increased. For the case of manufacturing a porous SOG film on a substrate according to the above embodiment (without oxygen plasma treatment) In the case of manufacturing a porous SiO2 film on a substrate by the traditional technique (the method of silylation of inorganic SOG), the description of the invention is -30- 509997 A7 _B7 _ (28) (please read the back first) Please note this page and fill in this page again) Scanning electron microscope (SEM) to take a photograph of the cross-section, and observe the nature of the thin film of each porous membrane. From this SEM photograph, as in the case of Example 1, in the case of the conventional thin film, a large-diameter hole (several nm to several tens of nm) was observed, while the SOG film in the present invention is an extremely small hole. Actually, It is understood as a hole below 1 nm which cannot be observed by SEM. In addition, when lauryl trimethyl ammonium chloride (trade name: Kodaming 24P, manufactured by Kao Corporation) was used as the surfactant, it was also obtained with The same result as above. (Example 6: The fourth invention) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, using 0.7 mol of nitric acid with respect to 1 mol of TEOS, 12 mol of H02, 15 mol of ethanol, and a predetermined amount of interface The activator is used as a raw material for preparing a reaction solution for producing a porous Si02 film, and also prepares a Si02 solution for a porous SOG film. 0.1, 0.15, 0.2, and 0.25 of n-hexadecyltrimethylammonium chloride (manufactured by Kanto Chemical Co., Ltd., trade name: CTAC 1) added to TOES 1 mole as a surfactant, and prepared by coating liquid. Each coating solution was spin-coated on a semiconductor substrate (sample Nos. A1 to Η 1 ·) at a speed of 3000 rpm. Using a recognized infrared heating furnace, as shown in Table 5, the coated substrates are shown in Table 5. The first heat treatment step is performed at 200 ~ 400 ° C in air, followed by 100 ~ l (400 degrees in T5Pa atmosphere). C to perform the second heat treatment (baking treatment) step to obtain a hydrophobic porous Si02 film (Sample Nos. A5 to H5). As shown in Table 6, following the first step, 100 ~ 10_5Pa in an atmosphere of 3 50 ° C, 400 ° C, 450 ° C, and 500 ° C for the second heat treatment step to obtain a hydrophobic porous paper that is again applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) -31-509997 Α7 B7 V. Description of the invention (29) SiCh film (sample number 15 ~ L5). Time from the initial processing temperature of 200 ° C to the processing temperature of the next step of 400 ° C It is 60 minutes, and the heating rate is also the same in other cases. Although the heating rate is not particularly limited, it is better for the film material of the obtained film to have a small film ripple and a small leakage current. Also, vacuum firing The maintenance time in the process is not to produce a thin film structure The range of destruction is better, and it is fired for 30 minutes in this example. When the spectrum of the porous film obtained as described above is measured by FT-IR analysis, the same as the case in FIG. 3, there is no 3400 cm. · Absorption peak of 0H group near 1. For the obtained hydrophobic porous Si02 film (sample Nos. A5 to L5), an aluminum electrode was vapor-deposited, and then a specific permittivity measuring device (made by HP) was used ( RE IMPEDANCE ANALYZER 4191A) 'Measure the specific permittivity after ί week time. The obtained specific permittivity is shown in Table 5 and 6 «° (Please read the precautions on the back before filling this page) I Pack-Order The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS) A4 specification (210 × 297 mm) -32- 509997 A7 B7 V. Description of the invention (30) (Table 5) Sample number is initially Heat treatment (° C) Heat treatment CC of the next step) Surfactant / TEOS (Molar ratio) Specific permittivity (ε / £ 〇) A5 200 400 0.1 3.8 B5 200 400 0.15 3.2 C5 200 400 0.2 2.0 D5 200 400 0.25 1.5 E5 250 400 0, 25 1.5 F5 300 4 00 0.25 2.5 G5 350 400 0.25 3.2 H5 400 400, 0.25 4.1 (Please read the precautions on the back before filling out this page) The staff of the Intellectual Property Bureau of the Ministry of Economic Affairs printed by the cooperative, as known in Table 5, in the air with 200 ~ 350 ° C treatment, followed by 400 ° C treatment in a vacuum, gives an SOG film with a low specific permittivity in the range of 1.0 to 4.0. In addition, in the semiconductor process, even when other thin films are laminated thereon by CVD or the like, the dielectric constant is generally not increased. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)-.-509997 A7 B7 V. Description of the invention (31) (Table 6) Sample number Initial heat treatment (° C) In the next step Heat treatment (° C) Surfactant / TE0S (Molar ratio) Specific permittivity (£ / £ 〇) 15 200 350 0.25 2.8 J5 250 400 0.25 1.7 K5 300 450 0.25 2.2 L5 350 5 00 0.25 3.0 (please first Read the notes on the back and fill in this page.) As you know in Table 5, understand that when it is processed at 200 ~ 350 ° C in air, and then at 350 ~ 450 ° C in vacuum, it has a low of 4.0 or less. Specific permittivity of SOG film. As known from the FT-IR spectrum, the absence of an OH-based spectrum means that there is no absorption of moisture due to the OH group, and that the wiring does not corrode A1 and the like. Furthermore, in the case of oxygen-plasma-treated hydrophobic porous SOG films, even when other thin films are laminated on top of them during the semiconductor process, their dielectric constants have not increased significantly. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the case where a porous SOG film is manufactured on a substrate according to this example (Sample No. 5), and the conventional technology (the method of silylation of inorganic SOG on the substrate) is used on the substrate In the case of manufacturing a porous Si02 film, a photograph of the cross section was taken with a scanning electron microscope (SEM), and the properties of the thin film of each porous film were observed. From this SEM photograph, as in the case of Example 1, in the case of the conventional thin film, a large-diameter hole (several nm to several tens of nm) was observed, while the SOG film in the present invention is an extremely small hole. Actually, It is understood as a hole below 1 nm which cannot be observed by SEM. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -34- 509997 A7 B7 V. Description of the invention (32) Also 'in the use of lauryl trimethyl ammonium chloride (made by Kao Corporation), commodity Name: Kou Daming 24P) In the case of replacing n-hexadecyl trimethyl chloride as a surfactant, the same results as above were obtained. [Industrial Applicability] As described above, the method for manufacturing the porous SOG film of the present invention is when an interlayer insulating film is used to form a field of a semiconductor process such as an LSI. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -35-