TWI358427B - - Google Patents

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13584271358427

九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種二氧化矽系被膜形成用組成物 二氧化矽系被膜。更詳言之，係有關於一種能夠在低溫 成被膜之二氧化矽系被貘形成用組成物及二氧化矽系 膜。 【先前技術】 二氧化矽系被膜多或舌組成物，係用以形成二氧化 系被膜，主要使用於丰導馥的配線等的段差缓和或配線 的溝填埋。因為是塗钸：¾體，即便是晶圓上的圖案凹處 能夠容易地填埋，所以萣夠以再現性良好的方式進行配 的平坦化。而且，該二氧化矽系被膜特別適合使用作為 間絕緣膜。 此種二氧化矽系枝裒通常能夠藉由將二氧化矽系被 形成用組成物塗佈在基板上，再於80°C〜3 00°C加熱，及 3 5 0 °C以上的溫度焙燒來彤成（例如，參照專利文獻1)。 [專利文獻1]曰本特開2005- 1 7 1 067號公報 及 形 被 矽 間 亦 線 層 膜 在 【發明内容】 [發明所欲解決之課题ΐ 如上述，因為必考！ 350 °C以上的高溫進行焙燒處 而導致生產力低落*又‘由於在高溫進行焙燒，致與矽 結之有機基分解等-在發揮二氧化矽系被膜之需要特 上，這並非良好的修存s 理 鍵 性 5 1358427 鑒於上述課題，本發明之目的係提俣一種藉由在低溫 加熱，便能夠形成二氧化矽系被膜之二氧化矽系被膜形成 用組成物。 [解決課題之手段][Technical Field] The present invention relates to a cerium oxide-based coating composition for forming a cerium oxide-based coating film. More specifically, it relates to a composition for forming a cerium oxide-based cerium which can form a coating film at a low temperature and a cerium oxide-based film. [Prior Art] A cerium oxide-based coating or a tongue composition is used to form a oxidized coating, and is mainly used for gradation of wiring such as wiring of a lead-in raft or trench filling of wiring. Since it is a coating: 3⁄4 body, even if the pattern recess on the wafer can be easily filled, it is flattened in such a manner that the reproducibility is good. Further, the ruthenium dioxide-based film is particularly suitably used as an interlayer insulating film. Such a cerium oxide-based branch can be usually coated on a substrate by a composition for forming a cerium oxide-based composition, heated at 80 ° C to 300 ° C, and calcined at a temperature of 350 ° C or higher. (For example, refer to Patent Document 1). [Patent Document 1] Unexamined-Japanese-Patent No. 2005- 1 7 1 067 and a film of a layered film are also [invention] [The problem to be solved by the invention] As described above, it is necessary to test! The calcination at a high temperature of 350 °C or higher results in low productivity*, and the calcination at high temperatures causes decomposition of the organic group with the ruthenium--the need to exert the ruthenium dioxide-based coating, which is not a good repair. In the light of the above-mentioned problem, the object of the present invention is to provide a composition for forming a cerium oxide-based film which can form a cerium oxide-based coating film by heating at a low temperature. [Means for solving the problem]

本發明者為了解決上述課題，著眼於添加於二氧化矽 系被膜形成用組成物中之添加劑而重複專心研討。結果， 發現使用藉由熱的作用產生脫水或脫醇反應之化合物，能 夠解決上述課題，而完成了本發明。更具璧达，本發明係 提供以下之物。 本發明的第一發明係提供一種二氧化穸系被膜形成用 組成物，係含有矽氧烷聚合物（A)、及籍甴多的作用產生脫 水或脫醇反應之化合物（B)而構成。 又，本發明的第二發明係使用前述二氣化矽系被膜形 成用組成物而得到之二氧化矽系被膜。 [發明之效果]In order to solve the above problems, the inventors of the present invention have focused on the additives added to the composition for forming a cerium oxide film. As a result, it has been found that the above problems can be solved by using a compound which produces a dehydration or dealcoholization reaction by the action of heat, and the present invention has been completed. More specifically, the present invention provides the following. According to a first aspect of the invention, there is provided a composition for forming a cerium oxide-based film comprising a siloxane polymer (A) and a compound (B) which causes dehydration or dealcoholization reaction by a large amount of action. Further, the second invention of the present invention is a cerium oxide-based coating obtained by using the composition for forming a bismuth oxide-based coating film. [Effects of the Invention]

本發明之二氧化矽系被膜形成用组戌场，含有藉由熱 的作用產生脫水或脫醇反應之化合物。籍此，能夠在不到 350 °C的溫度，便能夠容易地形成二氧化矽系被膜。 【實施方式】 以下，說明有關本發明之實施形S : 《二氧化矽系被膜形’成用組成物〉 本發明之二氧化矽系被膜形成用梃主赛係，含有矽氧 烷聚合物（A)、及藉由熱的作用產生脫永或叟醇反應之化合 物（B)而構成。 6 1358427 <矽氧烷聚合物（A)> 本發明之矽氧烷聚合物（A)(以下，亦稱為「（A)成 分」），沒有特別限定，係具有Si-Ο-Si鍵之聚合物。 該矽氧烷聚合物（A)之中，能夠以使用烧氧基矽烷之加 水分解縮合物為佳。上述烷氧基矽烷，能夠使用所有種類 的烷氧基矽烷。此種烷氧基矽烷可舉出的有例如下述通式 (a)所示之化合物。The cerium oxide-based film for forming a film of the present invention contains a compound which generates a dehydration or dealcoholization reaction by the action of heat. Thereby, the cerium oxide-based coating film can be easily formed at a temperature of less than 350 °C. [Embodiment] The following describes the embodiment of the present invention: "The composition of the cerium oxide-based coating film" is a main component of the cerium oxide-based coating film of the present invention, and contains a siloxane polymer ( A) and a compound (B) which generates a de- or sterol reaction by the action of heat. 6 1358427 <Heterosiloxane polymer (A)> The azoxyalkyl polymer (A) (hereinafter also referred to as "(A) component)) of the present invention is not particularly limited, and has Si-Ο-Si. The polymer of the bond. Among the siloxane polymers (A), a hydrolyzed condensate using a oxyalkylene oxide can be preferably used. As the above alkoxydecane, all kinds of alkoxydecane can be used. The alkoxydecane may, for example, be a compound represented by the following formula (a).

[化學式1] R2m-Si(OR3)4.m …⑷ (式中，R2係表示氫、碳數1〜20的烷基或芳基，R3係1價 的有機基，m係0〜2的整數）。R2m-Si(OR3)4.m (4) (wherein R2 represents hydrogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, R3 is a monovalent organic group, and m is 0 to 2; Integer).

在此，作為1價的有機基，可舉出的有例如烷基、芳 基、烯丙基、環氧丙基。此等之中，以烷基及芳基為佳。 烷基的碳數以1〜5為佳，可舉出的有例如曱基、乙基、丙 基、丁基等。又，烷基可以是直鏈狀亦可以是分枝狀，氫 亦可被氟取代。芳基以碳數6〜20之物為佳，可舉出的有 例如笨基、萘基等》 上述通式（a)所示化合物之具體例係 (al) m = 0時，可舉出的有四甲氧基矽烷、四乙氧基矽 烷、四丙氧基矽烷、四丁氧基矽烷等， (a2)m=l時，可舉出的有一曱基三曱氧基矽烷、一妄 基三乙氧基矽烷、一曱基三丙氧基矽烷、一乙基三曱氧基 矽烷、一乙基三乙氧基矽烷、一乙基三丙氧基矽烷、一 s 基三曱氧基矽烷、一丙基三乙氧基矽烷等的一烷基三烷氣 7 1358427 基矽烷、一苯基三甲氧基矽炼、一苯基三乙氧基矽烷等的 一苯基三烷氧基矽烷等，Here, examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Among these, an alkyl group and an aryl group are preferred. The alkyl group preferably has 1 to 5 carbon atoms, and examples thereof include a mercapto group, an ethyl group, a propyl group, and a butyl group. Further, the alkyl group may be linear or branched, and hydrogen may be substituted by fluorine. The aryl group is preferably a carbon number of 6 to 20, and examples thereof include a strepyl group, a naphthyl group, etc., and a specific example of the compound represented by the above formula (a) (al) m = 0, which may be mentioned There are tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, etc., when (a2) m = 1, a fluorenyl trimethoxy decane, a fluorene Triethoxy decane, monodecyltripropoxydecane, monoethyltrimethoxy decane, monoethyltriethoxydecane, monoethyltripropoxydecane, monos-tridecyloxy Monoalkyltrioxane gas such as decane, monopropyltriethoxydecane, etc. 7 1358427 decane, monophenyltrimethoxy oxime, monophenyltrialkoxydecane, monophenyltriethoxydecane, etc. Wait,

(a3) m = 2時，可舉出的有二甲基二甲氧基矽烷、二甲 基二乙氧基矽烷、二甲基二丙氧基矽烷、二乙基二曱氧基 矽烷、二乙基二乙氧基矽烷、二乙基二丙氧基矽烷、二丙 基二甲氧基矽烷、二丙基二乙氧基矽烷、二丙基二丙氧基 矽烷等的二烷基二烧氧基矽炫、二苯基二曱氧基矽烷、二 苯基二乙氧基矽烷等的二苯基二烷氧基矽烷等。 在本發明之二氧化矽系被膜形成用組成物，矽氧烷聚 合物（A)的重量平均分子量以2 00以上500 00以下為佳，以 1000以上3000以下為更佳。在此範圍時，能夠提高二氧 化矽系被膜形成用組成物的塗佈性。 烷氧基矽烷的加水分解縮合，能夠藉由使聚合單體之 烷氧基矽烷，在有機溶劑中，於酸觸媒或驗觸媒的存在下， 進行反應而得到。聚合單體之烷氧基矽烷，可只使用1種， 亦可組合二種以上來進行縮合。(a3) When m = 2, there may be mentioned dimethyl dimethoxydecane, dimethyl diethoxy decane, dimethyl dipropoxy decane, diethyl dimethoxy decane, and Dialkyldiones such as ethyldiethoxydecane, diethyldipropoxydecane, dipropyldimethoxydecane, dipropyldiethoxydecane, dipropyldipropoxydecane, etc. A diphenyl dialkoxy decane such as oxoxane, diphenyldimethoxy decane or diphenyldiethoxy decane. In the composition for forming a cerium oxide-based film of the present invention, the weight average molecular weight of the siloxane polymer (A) is preferably 200 or more and 500 or less, more preferably 1,000 or more and 3,000 or less. In this range, the coatability of the composition for forming a ruthenium oxide film can be improved. The hydrolyzation condensation of the alkoxydecane can be obtained by reacting an alkoxysilane of a polymerization monomer in an organic solvent in the presence of an acid catalyst or a catalyst. The alkoxysilane of the polymerization monomer may be used singly or in combination of two or more kinds.

又，亦可在加水分解時添加三甲基曱氧基矽烷、三曱 基乙氧基矽烷、三甲基丙氧基矽烷、三乙基甲氧基矽烷、 三乙基乙氧基矽烷、三乙基丙氧基矽烷、三丙基甲氧基矽 烷、三丙基乙氧基矽烷等的三烷基烷氧基矽烷；三苯基甲 氧基矽烷、三苯基乙氧基矽烷等的三苯基烷氧基矽烷等。 成為縮合的前提條件之烷氧基矽烷的加水分解程度， 能夠藉由添加的水量來調整。通常係相對於前述化學式（a) 所示之院氧基妙烧的合計莫耳數，使水的添加量為 8 1358427 1.0〜10.0倍莫耳為佳，以1.5〜8.0倍莫耳的比例為更佳。 藉由使水的添加量為1.0倍莫耳以上，能夠充分地增大加 水分解度，能夠良好地形成被膜。另一方面，藉由在10.0 倍莫耳以下，能夠防止凝膠化，能夠使保存安定性良好。Further, trimethyl decyloxydecane, trimethyl ethoxy decane, trimethyl propoxy decane, triethyl methoxy decane, triethyl ethoxy decane, and the like may be added at the time of hydrolysis. a trialkyl alkoxy decane such as ethyl propyl decane, tripropyl methoxy decane or tripropyl ethoxy decane; three triphenyl methoxy decane, triphenyl ethoxy decane, etc. Phenyl alkoxy decane and the like. The degree of hydrolysis of the alkoxydecane which is a prerequisite for the condensation can be adjusted by the amount of water added. Usually, it is a molar amount of the total amount of the molars of the oxylates shown in the above formula (a), and the amount of water added is preferably 8 1358427 1.0 to 10.0 times the molar amount, and the ratio is 1.5 to 8.0 times the molar amount. Better. By adding the amount of water to 1.0 times or more, the degree of hydrolysis can be sufficiently increased, and the film can be formed favorably. On the other hand, gelation can be prevented by 10.0 times or less, and storage stability can be improved.

又，化學式（a)所示之烧氧基石夕院的縮合，以使用酸觸 媒為佳，所使用的酸觸媒沒有特別限定，能夠使用先前常 被使用之有機酸、無機酸中任一種。有機酸可舉出的有乙 酸、丙酸、丁酸等有機羧酸；無機酸可舉出的有鹽酸、硝 酸、硫酸、磷酸等。酸觸媒可直接添加在烷氧基矽烷與水 之混合物中；又，亦可與水一同作為酸性水溶液而添加在 烷氧基矽烷中。In addition, it is preferable to use an acid catalyst for the condensation of the alkoxy sulphate represented by the chemical formula (a), and the acid catalyst to be used is not particularly limited, and any of the organic acids and inorganic acids which have been conventionally used can be used. . The organic acid may, for example, be an organic carboxylic acid such as acetic acid, propionic acid or butyric acid; and the inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid. The acid catalyst may be directly added to the mixture of alkoxy decane and water; or it may be added to the alkoxy decane as an acidic aqueous solution together with water.

加水分解反應係通常在5〜1 0 0小時左右完成。又，在 室溫至未超過80 °C之加熱溫度，藉由將酸觸媒水溶液滴加 在含有化學式（a)所示之1種以上的烧氧基妙烧之有機溶劑 中，亦能夠在較短的反.應時間完成反應。已加水分解的烷 氧基矽烷隨後產生缩合反應，結果，形成Si-O-Si之網狀 結構。 <藉由熱作用產生脫水或脫醇反應之化合物（B)> 藉由熱的作用產生脫水或脫醇反應之化合物（以下亦 稱為「（B)成分」），只要能夠藉由加熱來促進上述（A)成分 產生脫水反應、或是脫醇反應時，便可以使用而沒有特別 限定。 將藉由熱的作用產生脫水或脫醇反應之化合物添加在 二氧化矽被膜形成用組成物中，能夠以未在例如350t以上 9 1358427 的高温進行焙燒的方式來形成二氧化矽系被膜。藉此，能 夠使塗佈二氧化矽系被膜形成周组成物後之加熱（例如，乾 燥、焙燒）簡略化。 此種物質以具有異氰酸酯基之矽化合物為佳，以下述 通式（b)所示之化合物為更佳。 [化學式2] R]n-Si(NCO)4-n •••(b)The hydrolysis reaction system is usually completed in about 5 to 100 hours. Further, it is also possible to add an acid catalyst aqueous solution to the organic solvent containing one or more kinds of the alkyloxylates represented by the chemical formula (a) at room temperature to a heating temperature of not more than 80 °C. The shorter one should complete the reaction in time. The hydrolyzed alkoxysilane is then subjected to a condensation reaction, and as a result, a network structure of Si-O-Si is formed. <Compound (B) which produces a dehydration or dealcoholization reaction by thermal action> A compound which produces a dehydration or dealcoholization reaction by heat (hereinafter also referred to as "(B) component)", as long as it can be heated When the dehydration reaction or the dealcoholization reaction of the component (A) is promoted, it can be used without particular limitation. A compound which forms a dehydration or dealcoholization reaction by the action of heat is added to the composition for forming a cerium oxide film, and the cerium oxide-based coating film can be formed by baking at a high temperature of, for example, 350 t or more and 1 1358427. Thereby, heating (e.g., drying, baking) after the formation of the composition of the ceria-based coating film can be simplified. Such a substance is preferably a ruthenium compound having an isocyanate group, and more preferably a compound represented by the following formula (b). [Chemical Formula 2] R]n-Si(NCO)4-n •••(b)

(式中，R1係表示碳數1〜10的烷基，η係0〜3的整數）。 上述通式（b)所示之化合物可舉出的有四異氰酸酯基 矽烷、曱基三異氰酸酯基矽烷、乙基三異氰酸酯基矽烷、 丙基三異氰酸酯基矽烷、丁基三異氰酸酯基矽烷、二甲基 二異氰酸酯基矽烷、二乙基二異氰酸酯基矽烷、二丙基二 異氰酸酯基矽烷、二丁基二異氰酸趋基矽烷、三甲基異氰 酸酯基矽烷、三乙基異氰酸酯基矽烷、三丙基異氰酸酯基 矽烷、三丁基異氰酸酯基矽烷等。(In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms, and η is an integer of 0 to 3). The compound represented by the above formula (b) may, for example, be a tetraisocyanate decane, a decyl triisocyanate decane, an ethyl triisocyanate decane, a propyl triisocyanate decane, a butyl triisocyanate decane or a dimethyl group. Diisocyanate decane, diethyl diisocyanate decane, dipropyl diisocyanate decane, dibutyl diisocyanate decane, trimethyl isocyanate decane, triethyl isocyanate decane, tripropyl Isocyanate decane, tributyl isocyanate decane, and the like.

又，此等的（B)成分，可單獨使用一種，亦可組合使用 2種以上。 相對於（A)成分之Si02換算質量，（B)成分之含量以0.1 質量％以上20質量％以下為佳，以0 · 5質量％以上1 5質量 %以下為更佳。藉由使（B)成分在上述範圍，能夠提高二氧 化矽系被膜形成用組成物之經時安定性。 <其他成分> (界面活性劑） 本發明之二氧化矽系被膜形成用组成物，較佳為調配 10 1358427 有界面活性察為佳。藉由界面活性劑的存在，能夠提升對 基板的塗佈性及展開性。 (溶劑）In addition, these (B) components may be used alone or in combination of two or more. The content of the component (B) is preferably 0.1% by mass or more and 20% by mass or less based on the SiO 2 conversion mass of the component (A), and more preferably 0.5% by mass or more and 15% by mass or less. By setting the component (B) in the above range, the stability with time of the composition for forming a cerium oxide-based film can be improved. <Other components> (Surfactant) The composition for forming a cerium oxide-based film of the present invention is preferably formulated to have an interface activity of 10 1358427. The coating property and the spreadability to the substrate can be improved by the presence of the surfactant. (solvent)

為了提升塗佈性及膜厚度均勻性之目的，本發明之二 氧化矽系被膜形成用組成物以含有溶劑為佳。該溶劑能夠 使用先前通f使用之有機溶劑。具體例可舉出的有如曱 醇、乙醇、乓赛、丁醇、3 -曱氧基-3-曱基-1-丁醇、3 -曱氧 基-1-丁醇之一元醇；如 3 -曱氧基丙酸曱酯、3 -乙氧基丙 酸乙酯之汔基羧酸酯；如乙二醇、二甘醇、丙二醇之多元 醇；如乙二择一甲基醚、乙二醇一乙基醚、乙二醇一丙基 醚、乙二醇一 丁基醚、丙二醇一曱基醚、丙二醇一乙基鲢、 丙二醇一丙基Μ、丙二醇一丁基醚、乙二醇一曱基醚乙酸 酯、乙二醇一乙基醚乙酸醋、丙二醇一曱基醚乙酸酯、丙 二醇一乙基醚乙酸酯之多元醇衍生物；如乙酸、丙酸之脂 肪酸；丙酮、曱基乙基酮、2-庚酮之酮等。此等之中，以 使用醇系、兮醇系的溶劑為佳。又，此等有機溶劑可單獨 使用，亦可组合使用2種以上。 該等溶赛的量沒有特別限定，使溶劑以外的成分（固體 成分）的濃度皂5~100質量％為佳，以20~50質量％為更佺。 藉由在這萣藿？3，能夠提高塗佈性。 (其他） •又，圣又發明，於不損害本發明效果的範圍内，鉅夠 調配其他吴秦室、添加劑等。 11 1358427 《二氧化矽系被膜的形成方法〉 二氧化矽系被膜的形成方法，首先係將二氧化矽系被 膜形成用组成物塗佈在基板上。將二氧化矽系被膜形成用 組成物塗佈在基板上之方法，能夠使用例如喷灑法、旋轉 塗佈法、浸潰法、輥塗法等任意的方法，通常使用旋轉塗 佈法。In order to improve the coating property and the uniformity of the film thickness, the composition for forming a cerium oxide-based film of the present invention preferably contains a solvent. This solvent can use the organic solvent previously used. Specific examples include, for example, decyl alcohol, ethanol, table tennis, butanol, 3-methoxy-3-mercapto-1-butanol, and 3-methoxy-1-butanol; - decyl methoxy propionate, decyl carboxylate of ethyl 3-ethoxypropionate; polyol such as ethylene glycol, diethylene glycol, propylene glycol; such as ethylene dimethyl ether, ethylene Alcohol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monodecyl ether, propylene glycol monoethyl hydrazine, propylene glycol monopropyl hydrazine, propylene glycol monobutyl ether, ethylene glycol a polyhydric alcohol derivative of mercaptoether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate; a fatty acid such as acetic acid or propionic acid; acetone, Mercaptoethyl ketone, 2-heptanone ketone, and the like. Among these, it is preferred to use an alcohol-based or decyl alcohol-based solvent. Further, these organic solvents may be used singly or in combination of two or more. The amount of the solvent is not particularly limited, and the concentration of the component (solid content) other than the solvent is preferably 5 to 100% by mass, and more preferably 20 to 50% by mass. With this here? 3, can improve the coating properties. (Others) • In addition, St. is invented, and within the scope that does not impair the effects of the present invention, it is possible to allocate other Wuqin chambers, additives, and the like. 11 1358427 "Method for forming a cerium oxide-based coating film" A method for forming a cerium oxide-based coating film is to apply a composition for forming a cerium oxide-based coating film onto a substrate. The method of applying the composition for forming a cerium oxide-based film onto a substrate can be carried out by any method such as a spray method, a spin coating method, a dipping method or a roll coating method, and a spin coating method is usually used.

接著，對已塗佈在基板上a二氧化矽系被膜形成用組 成物進行加熱處理。加熱處理之手段 '溫度、時間等沒有 特別限制，通常可在80〜3 00t主右的熱板上加熱1~6分鐘 左右。 依照本發明之二氧化矽系S粜形成用組成物時，藉由 加熱處理，（B)成分能夠促進（A)戎分之脫水或脫醇反應。因 為藉由該脫水或脫醇反應，訖尧彤成S i - Ο - S i之網狀結構， 所以能夠得到細緻的二氧化矽杗被膜。Next, the composition for forming a cerium oxide-based film which has been applied onto the substrate is subjected to heat treatment. The means of heat treatment 'temperature, time, etc. are not particularly limited, and can usually be heated on a hot plate of 80 to 300 00 main right for about 1 to 6 minutes. According to the composition for forming a cerium oxide-based cerium of the present invention, the component (B) can accelerate the dehydration or dealcoholization reaction of (A) by heat treatment. Since the dehydration or dealcoholization reaction is carried out to form a network structure of S i - Ο - S i , a fine ruthenium dioxide film can be obtained.

又，加熱處理以3階段以上為佳，以階段地升溫為佳。 具體上，係於大氣中或氮等楕拴氣體環境下，在 60〜150 。(：左右的熱板上，進行30秒~2分鐘左右之第1次加熱處 理後，在100〜2 2(TC左右的熱S上，進行30秒〜2分鐘左 右之第2次加熱處理後，進面在150〜300 °C左右的熱板上， 進行30秒~2分鐘左右之第？之釦熱處理。藉由如此地進 行 3階段以上、較佳是 3-5*孜左右之階段式的加熱處 理，能夠以較低的溫度來形或二I化矽系被膜。 [實施例] 接著，基於實施例，更諄每地說明本發明，但是本發 12 1358427 明未被限定於這些實施例。 〈實施例1 &gt;Further, the heat treatment is preferably three or more stages, and it is preferred to increase the temperature in stages. Specifically, it is in the atmosphere or in a helium gas atmosphere such as nitrogen, at 60 to 150 Å. (: On the left and right hot plates, after the first heat treatment for about 30 seconds to 2 minutes, after the second heat treatment for about 30 seconds to 2 minutes on the heat S of about TC (about TC) And the surface is heated on a hot plate of about 150 to 300 ° C for about 30 seconds to 2 minutes, and the stage heat treatment is performed in three stages or more, preferably about 3-5*孜. The heat treatment can form a bismuth film at a lower temperature. [Examples] Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these embodiments. Example <Example 1 &gt;

對以三烷氧基碎坑的加水分解生成物作為主成分之旋 塗式玻璃（Spin-On Glass)材料（OCDT-12 1000V(商品名）： 東京應化工業（股）製、換算Si02之固體成分濃度：7質量 %)，以相對於旋塗式玻璃材料中的固體成分為1 f量％的 方式添加上述四異氰酸酯基矽烷，來製造二氧亡兰杗被膜 形成用組成物。使用塗佈器（SS8261NUU:東京恿二業（股） 製），以旋轉數lOOOrpm將二氧化矽系被膜形成角a成物塗 佈在6英吋的矽晶圓上。接著，於熱板上在801進行加熱 60秒鐘、在1 50°C加熱60秒鐘、在200°C加熱60秒鐘， 來形成二氧化矽系被膜。 〈比較例1 &gt; 使用OCD T- 1 2 1 000V，藉由與實施例1同樣约方法， 來製造二氧化矽系被膜。 〈比較例2 &gt;Spin-On Glass material (OCDT-12 1000V (trade name): manufactured by Tokyo Chemical Industry Co., Ltd., converted to Si02, which is a main component of a hydrolyzed product of a trialkoxy slag. In the solid content concentration: 7% by mass, the tetraisocyanate-based decane is added to the solid content of the spin-on glass material in an amount of 1% by volume to produce a composition for forming a dioxanil film. Using a coater (SS8261NUU: manufactured by Tokyo Seiki Co., Ltd.), the cerium oxide-based film forming angle a was coated on a 6-inch ruthenium wafer at a number of revolutions of 100 rpm. Subsequently, the film was heated at 801 for 60 seconds on a hot plate, heated at 150 ° C for 60 seconds, and heated at 200 ° C for 60 seconds to form a cerium oxide-based film. <Comparative Example 1 &gt; A cerium oxide-based coating film was produced by the same method as in Example 1 using OCD T-1 2 1 000 V. <Comparative Example 2 &gt;

在比較例1，加熱後更在氮氣環境下在4 0 0 u進行培 燒，來形成二氧化矽系被膜。 &lt;成膜性評價&gt; 成膜性評價係使用FT-IR(FTIR-615(商品名v: 3本分 光股份公司製）來進行，藉由Si-Ο鍵的尖鋒面薄籌Si- H鍵 的尖鋒面積之比來進行評價。又，在FT-IR圖，三1550cm·1 附近的尖鋒係表示Si-0鍵，在2250 cnT1附近钤矢鋒係表 示Si-H鍵 '结果如表1所示。又，實施例1之FT-IR圖係 13 1358427 如第1圖所示，比較例1之FT-IR圖係如第2圖所示。 [表1] 膜厚度（A) Si-0/Si-H 實施例1 459 1 3.131 比較例1 43 25 2.364 比較例2 4340 3.164In Comparative Example 1, after heating, it was incubated at 400 Torr in a nitrogen atmosphere to form a cerium oxide-based coating. &lt;Evaluation of film formation property&gt; The evaluation of the film formation property was carried out by using FT-IR (FTIR-615 (trade name: 3 manufactured by Seiko Co., Ltd.), and Si-H was thinned by the tip of the Si-Ο bond. The ratio of the tip area of the bond is evaluated. Also, in the FT-IR diagram, the spikes near the three 1550 cm·1 indicate the Si-0 bond, and the vicinity of the 2250 cnT1 indicates that the Si-H bond results in the Further, the FT-IR chart of the first embodiment is 13 1358427. As shown in Fig. 1, the FT-IR chart of Comparative Example 1 is as shown in Fig. 2. [Table 1] Film thickness (A) Si-0/Si-H Example 1 459 1 3.131 Comparative Example 1 43 25 2.364 Comparative Example 2 4340 3.164

根據表1，與未添加添加劑（四異氰酸酯基带院）之比較 例1比較時，能夠確認添加有添加劑之實施例1，藉由在 200°C以下的加熱，能夠形成Si-0-Si的網狀結構。又，與 在 400 °C進行焙燒之比較例 2比較時，具有相同程度的 S i - Ο / S i - Η比，確認所形成的S i - Ο - S i網狀結構與進行焙燒 時比較，係同等的。 【圖式簡單說明】 第1圖係顯示實施例1之FT-IR的圖。 第2圖係顯示比較例1之FT-IR的圖。According to Table 1, when compared with Comparative Example 1 in which no additive (tetraisocyanate base) was added, it was confirmed that Example 1 in which an additive was added, and a network of Si-0-Si could be formed by heating at 200 ° C or lower. Structure. Further, when compared with Comparative Example 2 which was calcined at 400 ° C, the S i - Ο / S i - Η ratio was the same, and it was confirmed that the formed S i - Ο - S i network structure was compared with the calcination. , the same. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the FT-IR of the first embodiment. Fig. 2 is a view showing the FT-IR of Comparative Example 1.

【主要元件符號說明】 無 14[Main component symbol description] None 14

Claims (1)

13584271358427 丨公告本I 第 十、申請專利範圍： 1S 修正本j 1 · 一種二氧化矽系被膜形成用組成物，係含有矽氧烧聚 合物（A)、及藉由熱的作用產生脫水或脫醇反應之化合物（B) 而構成’ 該矽氧烷聚合物（A)係烷氧基矽烷的加水分解縮合物， 該化合物（B)係下述通式（b)所表示之化合物， R1n-Si(NC0)4-„ -..(b)丨Announcement I Tenth, the scope of application: 1S Revision j 1 · A composition for forming a cerium oxide film, which contains a cerium-oxygenated polymer (A) and dehydration or dealcoholization by the action of heat The compound (B) to be reacted to form a hydrolyzed condensate of the alkoxyalkyl polymer (A) which is a compound represented by the following formula (b), R1n-Si (NC0)4-„ -..(b) (式中，R1係碳數1〜1〇的烷基，η係〇〜3的整數） 相對於（Α)成分之SiCh換算質量，該化合物（Β)之含量 為〇丨質量％以上2 0質量％以下。 2.如申請專利範圍第1項所述之二氧化矽系被膜形成用 組成物，其中該炫氧基發烧係含有至少1種選自下述通式 (a)所示之化合物， R2m-Si(〇R3)4m *··(&amp;) (式中，R2係表示氫、碳數^20的烷基或芳基，R3係1價 的有機基，m係0〜2的整數）。 3 一種二氧化矽系被臈，係使用如申請專利範圍第丨項 所述之二氧化矽系被膜形成用組成物而得到。 15(In the formula, R1 is an alkyl group having 1 to 1 ring carbon number, and an integer of η is 〇 〜3). The content of the compound (Β) is 〇丨% by mass or more based on the SiCh equivalent mass of the (Α) component. Below mass%. 2. The composition for forming a cerium oxide-based film according to the first aspect of the invention, wherein the oxy-oxygen-containing system contains at least one compound selected from the group consisting of the following formula (a), R2m- Si (〇R3) 4m * (&amp;) (wherein R2 represents hydrogen, an alkyl group or an aryl group having a carbon number of 20, R3 is a monovalent organic group, and m is an integer of 0 to 2). (3) A cerium oxide-based cerium is obtained by using a composition for forming a cerium oxide-based film as described in the above-mentioned patent application. 15