201137155 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種釕膜形成用材料及釕膜形成方法。 【先前技術】 以DRAM (動態隨機存取記憶體）爲代表之半導體裝 置隨著其高積體化與微細化，有必要對構成裝置之各金屬 膜及金屬氧化膜之材料進行變更。 尤其，半導體裝置內之多層配線用途中正要求導電性 金屬膜之改良，而朝變換成新的導電性高的銅配線進展。 爲了提高該銅配線之導電性而在多層配線之層間絕緣膜材 料中使用低介電率材料（低-k材料）。然而，該低介電率 材料中所含之氧原子容易進入到銅配線中，而產生其導電 性下降之問題。因此，爲了防止來自低介電率材料之氧的 移動，而檢討在低介電率材料與銅配線之間形成障壁膜之 技術。至於於該障壁膜用途中使用之不易獲取來自介電體 層之氧的材料及可藉由乾蝕刻容易加工之材料，以金屬釕 膜備受矚目。再者在藉由電鍍法埋入上述銅配線之鑲嵌成 膜法中’自同時滿足上述障壁膜與電鍍成長膜二者之角色 而言，以金屬釕備受矚目。且，在半導體裝置之電容中， 作爲如氧化鋁、五氧化鉬、氧化給、鈦酸鋇•緦（B ST ) 之闻介電率材料之電極材料，金屬釘膜由於其高的耐氧化 性與高的導電性亦受到囑目。 上述金屬釕膜之形成，於以往大多使用濺鍍法，但近 -5- 201137155 年來作爲朝構造之微細化、薄膜化、量產性提高 則已檢討化學氣相沉積法。 然而，一般以化學氣相沉積法形成之金屬膜 集合狀態稀疏等，使表面形態變差，故檢討於化 積材料中使用參（二特戊醯基甲酸酯）釕 dipivaloylmethanato ) ruthenium ) 或二： Ruthenocene )、雙（烷基環戊二烯基）釕、（ 烯基）釕三羰基等作爲用以解決該形態問題之手 專利文獻1〜5 )。 再者，在製造步驟中使用該等化學氣相沉積 爲了防止成膜步驟中之金屬釕膜鄰接之材料劣化 製造條件，而要求材料良好的儲存安定性。然而 二茂釕或雙（烷基環戊二烯）釕等所具有之問題 驟中混合氧之影響，在短時間使鄰接之材料氧化 造成性能劣化。又，成膜步驟中未混合氧時，會 以成膜之問題。 另一方面，對釕膜要求爲高純度，作爲障壁 成長膜之優異性能’以及對基板優異之密著性。 [先前技術文獻] [專利文獻] [專利文獻1]特開平6-28 343 8號公報 [專利文獻2]特開平丨〗_3 5 5 89號公報 [專利文獻3]特開2002-114795號公報 之對策， 之微結晶 學氣相沉 (tris ( 笼釕 （ 二環己二 段（參照 材料時， ，穩定其 ，現有之 爲成膜步 及伴隨此 有釕膜難 膜及電鍍 201137155 [專利文獻4]特開2002-212112號公報 [專利文獻5]特開2006-24 1 55 7號公報 【發明內容】 [發明欲解決之課題] 本發明係鑑於上述問題而完成者，其目的係提供一種 即使在不存在氧等氧化劑之下仍容易分解，可在短時間成 膜高純度且對基板之密著性優異之釕膜的釕膜形成用材料 ，及使用該材料之釕膜形成方法。 [用以解決課題之手段] 爲達成上述目的，本發明人等進行積極的硏究，發現 藉由使用以下述式（1)表示之化合物可達成上述目的， 因而完成本發明。 亦即，本發明係提供下述[1]〜[6]者。 Π] —種釕膜形成用材料，其含有以下述式（1)表 示之化合物，201137155 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a material for forming a ruthenium film and a method for forming a ruthenium film. [Prior Art] As a semiconductor device represented by a DRAM (Dynamic Random Access Memory) is highly integrated and miniaturized, it is necessary to change the material of each metal film and metal oxide film constituting the device. In particular, in the use of multilayer wiring in a semiconductor device, improvement of a conductive metal film is required, and progress is made to convert into a new copper wiring having high conductivity. In order to improve the conductivity of the copper wiring, a low dielectric material (low-k material) is used in the interlayer insulating film material of the multilayer wiring. However, the oxygen atoms contained in the low dielectric material easily enter the copper wiring, causing a problem that the conductivity thereof is lowered. Therefore, in order to prevent the movement of oxygen from a low dielectric material, a technique of forming a barrier film between a low dielectric material and a copper wiring is reviewed. As a material for use in the barrier film which is difficult to obtain oxygen from the dielectric layer and a material which can be easily processed by dry etching, a metal ruthenium film is attracting attention. Further, in the inlaid film forming method in which the above-described copper wiring is buried by electroplating, the role of both the barrier film and the electroplated grown film is satisfied, and the metal is attracting attention. Moreover, in the capacitance of the semiconductor device, as an electrode material of a dielectric material such as alumina, molybdenum pentoxide, oxidized, barium titanate (BST), the metal nail film is highly resistant to oxidation due to its high resistance to oxidation. High conductivity is also attracting attention. In the formation of the above-mentioned metal ruthenium film, the sputtering method has been used in many cases. However, the chemical vapor deposition method has been reviewed as a result of miniaturization, thinning, and mass productivity of the structure. However, in general, the state of the metal film formed by the chemical vapor deposition method is sparse, and the surface morphology is deteriorated. Therefore, it is considered to use ginseng (di-pivalaphthalate) 钌dipivaloylmethanato) ruthenium or two in the chemical material. : Ruthenocene ), bis(alkylcyclopentadienyl)fluorene, (alkenyl)phosphonium tricarbonyl, etc., as a hand to solve this morphological problem, Patent Documents 1 to 5). Further, the use of the chemical vapor deposition in the production step requires a good storage stability of the material in order to prevent the deterioration of the material adjacent to the metal tantalum film in the film forming step. However, the influence of mixed oxygen in the problem of ferrocene or bis(alkylcyclopentadienyl) ruthenium causes oxidation of adjacent materials to deteriorate performance in a short time. Further, when oxygen is not mixed in the film forming step, there is a problem of film formation. On the other hand, the ruthenium film is required to have high purity, excellent performance as a barrier film, and excellent adhesion to a substrate. [Patent Document 1] JP-A-2002-114795 Countermeasure, microcrystallography gas phase sinking (tris (cage 二 (dicyclohexene two-stage (when referring to materials, stabilize it, the existing film forming step and accompanying enamel film and electroplating 201137155 [Patent Literature [Problem to be solved by the invention] The present invention has been made in view of the above problems, and an object thereof is to provide a Even in the absence of an oxidizing agent such as oxygen, it is easy to decompose, and a film for forming a ruthenium film having a high purity and excellent adhesion to a substrate can be formed in a short period of time, and a ruthenium film forming method using the material. In order to achieve the above object, the present inventors have conducted active research and found that the above object can be attained by using a compound represented by the following formula (1), thereby completing the present invention. Provide the following [1] ~ [6] Π] - ruthenium film forming seed material, the compound represented by the following formula (1) which comprises,
Ru ( PRS ) , ( L1 ) m ( L2 ) n ( 1 ) (上述式（1)中，R1各獨立爲氫原子、鹵素原子、碳數 1~4之烴基、或碳數1〜4之鹵化烴基，L1爲氫原子' 或鹵素 原子，L2爲具有至少兩個雙鍵之碳數4~ 10之不飽和烴化合 物’ 1爲1〜5之整數，m爲0〜4之整數，η爲0~2之整數，但， 201137155 l + m + 2n = 5或 6 ) » [2] 如前述[1]所述之釕膜形成用材料，其爲化學氣 相沉積法用。 [3] —種釕膜形成方法，其使用如前述[1]或[2]所述 之釕膜形成用材料》 [4] 一種釕膜形成方法，其係包含將如前述[2]所述 之釕膜形成用材料供給於基體上之釕膜形成用材料供給步 驟，及使該釕膜形成用材料加熱分解，於上述基體上形成 釕膜之膜形成步驟。 [5] 如前述[4]所述之釕膜形成方法，其中上述膜形 成步驟中之加熱分解溫度爲100 °C〜800 °C。 [6] 如前述[4]或[5]所述之釕膜形成方法，其中上述 膜形成步驟中之加熱分解係在惰性氣體或還原性氣體中進 行。 [發明效果] 本發明之釕膜形成用材料即使在沒有氧等氧化劑存在 下，仍可容易分解而形成釕膜。因此，鄰接材料之氧化及 伴隨此而產生之性能劣化之虞較小。 又，依據本發明之釕膜形成用材料，可在短時間容易 地獲得殘留雜質量少之高純度良質釕膜。該釕膜作爲障壁 膜及電鍍成長膜之性能優異，且，對基板之密著性亦優異 201137155 【實施方式】 以下，針對本發明詳細的說明。 本發明之釕膜形成用材料包含以下述式（1)表示之 化合物。Ru ( PRS ) , ( L1 ) m ( L2 ) n ( 1 ) (In the above formula (1), R 1 is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogen group having 1 to 4 carbon atoms; a hydrocarbon group, L1 is a hydrogen atom' or a halogen atom, and L2 is an unsaturated hydrocarbon compound having 4 to 10 carbon atoms having at least two double bonds. '1 is an integer of 1 to 5, m is an integer of 0 to 4, and η is 0. [2] The material for forming a ruthenium film according to the above [1], which is used for the chemical vapor deposition method, is an integer of ～2. [3] A method for forming a ruthenium film, which comprises the material for forming a ruthenium film according to the above [1] or [2], [4] a method for forming a ruthenium film, which comprises the method of [2] as described in the above [2] The ruthenium film forming material is supplied to the substrate and the ruthenium film forming material is supplied to the substrate, and the ruthenium film forming material is thermally decomposed to form a ruthenium film forming step on the substrate. [5] The method for forming a ruthenium film according to the above [4], wherein the heat decomposition temperature in the film forming step is from 100 ° C to 800 ° C. [6] The method for forming a ruthenium film according to the above [4] or [5] wherein the thermal decomposition in the film formation step is carried out in an inert gas or a reducing gas. [Effect of the invention] The material for forming a ruthenium film of the present invention can be easily decomposed to form a ruthenium film even in the absence of an oxidizing agent such as oxygen. Therefore, the oxidation of the adjacent material and the performance deterioration associated therewith are small. Further, according to the material for forming a ruthenium film of the present invention, a high-purity good ruthenium film having a small amount of residual impurities can be easily obtained in a short time. This ruthenium film is excellent in performance as a barrier film and a plated film, and is excellent in adhesion to a substrate. 201137155 [Embodiment] Hereinafter, the present invention will be described in detail. The material for forming a ruthenium film of the present invention contains a compound represented by the following formula (1).
Ru ( PRS) 1 ( L1) m ( L2) η ( 1 ) 上述式（1)中，R1各獨立爲氫原子、鹵素原子、碳 數之烴基、或碳數1〜4之鹵化烴基，較好爲鹵素原子、 碳數1〜4之烴基、或碳數1~4之鹵化烴基，更好爲鹵素原子 〇 R1中之鹵素原子列舉爲氟原子、氯原子、溴原子、碘 原子，較好爲氟原子、氯原子，更好爲氟原子。 又，R1中之碳數1〜4之烴基可列舉爲甲基、乙基、正 丙基、異丙基、正丁基、異丁基、第三丁基，較好爲甲基 、乙基、正丙基、異丙基、第三丁基，更好爲甲基、乙基 〇 又，R1中之碳數1~4之鹵化烴基較好爲氟化烴基、氯 化烴基、溴化烴基，更好爲氟化烴基。 具體而言可列舉爲氯甲基、二氯甲基、三氯甲基、氟 甲基、二氟甲基、三氟甲基、2，2,2-三氟乙基、五氟乙基 、全氟正丙基、全氟異丙基、全氟正丁基、全氟異丁基、 全氟第三丁基，較好爲氟甲基、二氟甲基、三氟甲基、 2,2,2-三氟乙基、五氟乙基、全氟正丙基、全氟異丙基、 201137155 全氟第三丁基，更好爲氟甲基、二氟甲基、三氟甲基、 2,2,2-三氟乙基、五氟乙基。 通式（1)中，L1爲氫原子、或鹵素原子，較好爲氫 原子。 L1爲鹵素原子時，該鹵素原子列舉爲氟原子、氯原子 、溴原子' 碘原子，較好爲氟原子、氯原子，更好爲氟原 子。 又’通式（1)中，L2爲具有至少兩個雙鍵之碳數 4~ 10之不飽和烴化合物。 具體而言可列舉爲1,3-戊二烯、1,5-己二烯、ι，4-己 二烯、1,3-己二烯、2,4-己二烯、3-甲基-1,3-戊二烯、2-甲基-1,4-戊二烯、1，6-庚二烯、1，5_庚二烯、ι，4_庚二烯 、1，7-辛二烯、1，6-辛二烯、1,5-辛二烯、l，4-辛二烯等鏈 狀二烯，1，5-環辛二烯、1，3-環辛二烯、l，4-環己二烯、 1，3-環己二烯等環狀二烯。 另外，通式（1)中，1爲1〜5之整數，就提高化合物 蒸氣壓之觀點而言，較好爲3〜5之整數。 又，通式（1 )中，m爲〇〜4之整數，就降低化合物熔 點之觀點而言’較好爲〇〜3之整數，更好爲〇~2之整數。 且’通式（1 )中’ η爲〇〜2之整數，就形成良質之純 度高的釘膜之觀點而言，較好爲〇或1，更好爲0。 再者，l + m + 2n = 5 或 6 以上述通式（1)表示之化合物之合成方法列舉爲包 含例如使三氯化釕與上述通式（1)中之以PR!3表示之化 -10- 201137155 合物反應之步驟之方法。 又’上述步驟中，亦可視需要使由氫、氟、氯、溴及 碘所選出之至少一種化合物，以及由上述通式（1)中之 以L2表示之具有至少兩個雙鍵之碳數4〜10之不飽和烴化合 物所選出之至少一種化合物反應。 上述反應較好在觸媒存在下進行，至於觸媒可列舉爲 例如銅、鋅等。 反應溫度並無特別限制，較好爲50〜400 °C，更好爲 100〜3 50°c，又更好爲 120°c 〜300°c。 且，反應時之壓力並無特別限制，但使三氟膦、氫、 氟、氯等在標準條件下爲氣體之化合物反應時，通常爲 10~1000氣壓（以下，亦稱爲「atm」），較好爲50~800氣 壓，更好爲1〇〇〜600氣壓。 以上述通式（1 )表示之化合物之具體例可列舉爲例 如以下之化合物等： 1 = 5，m = 0，n = 〇之化合物，爲伍（三氟膦）釕（〇 ) 、伍（三氯膦）釕（〇)、伍（三甲基膦）釕（0)、伍（ 三乙基膦）釕（0 )等釕之原子價爲〇之釕化合物； 1 = 3，111 = 0，11=1之化合物，爲（7?-1，4-環己二嫌）參 (三氟膦）釕（0) 、（ 7? -1,4-環己二烯）參（三甲基膦 )釕（〇) 、（1,5-環辛二烯）參（三氟膦）釕（0)、（ 1，5-環辛二烯）參（三甲基膦）釕（0 ) 、（77-1,6-庚二 烯）參（三氟膦）釕（0) 、（ 7? -1，6-庚二烯）參（三甲 基膦）釕（〇) 、（τ?-1，7-辛二烯）參（三氟膦）釕（0) -11 - 201137155 、（77-1，7-辛二烯）參（三甲基膦）釕（〇)等釕 價爲〇之釕化合物； 1 = 4’ m = 2，n = 0之化合物，爲二氫化肆（三氟 (II)、（二氟）肆（三氟膦）釕（II)、（二氯 三氟膦）釕（II )、二氫化肆（三甲基膦）釘（Π 二氟）肆（三甲基膦）釕（II)、（二氯）肆（三 )釕（Π )等釕之原子價爲2之釕化合物； 1 = 3，m = 3，n = 0之化合物，爲三氫化參（三氟 (III )、（三氟）參（三氟膦）釕（III )等釕之 爲3之釕化合物； 1 = 2，m = 4，n = 〇之化合物，爲四氫化雙（三氟 (IV)、（四氟）雙（三氟膦）釕（IV)、（四氯 三氟膦）釕（IV )、氫化（三氟）肆（三氟膦）釕 、二氫化（二氟）肆（三氟膦）釕（IV )、二氫化 )肆（三氟膦）釕（IV)、三氫化（氟）肆（三氟 (IV )、三氫化（碘）肆（三氟膦）釕（iv )等釕 價爲3之釕化合物；等。 該等化合物可單獨使用或混合兩種以上作爲釕 用材料使用。較好以單獨一種化合物作爲釕膜形成 使用。 本發明之釕膜形成方法爲使用上述釕膜形成用 方法者。 本發明之釕膜形成方法除使用上述釕膜形成用 外’亦可使用本身習知之方法，例如可採用如下述 之原子 膦）釕 )肆（ )' ( 甲基膦 膦）釕 原子價 膦）釕 )雙（ (IV) (二溴 膦）釕 之原子 膜形成 用材料 材料之 材料以 之化學 -12- 201137155 氣相沉積方法（包含下述步驟（1)及步驟（2)者）實施 〇 將本發明之釕膜形成用材料供給於基體（例如基板） 上’接著’使供給於基體上之釕膜形成用材料加熱分解， 於基體上形成釕膜。具體而言爲（1)在減壓及加熱下使 本發明之釘膜形成用材料氣化或蒸發，使其氣化物或蒸發 物堆積在基體（例如基板）上，接著，（2)使所得堆積 物加熱進行熱分解’於基體上形成釕膜。又，上述步驟（ 1)中’即使隨著本發明之釕膜形成用材料之分解，仍不 會減弱本發明之效果，可同時進行上述步驟（1)與上述 步驟（2 )。 此處使用之基體材料可使用例如玻璃、矽半導體、石 英、金屬、金屬氧化物、合成樹脂等適宜之材料，但較好 爲可耐受使釕化合物熱分解之溫度之材料。 上述步驟（1)中，使釕化合物氣化或蒸發之溫度較 好爲-100〜3 5 0°c ’更好爲-80〜200。(：，最好爲-60〜15〇r。 上述步驟（1)中，使釕化合物氣化或蒸發時之減壓 條件較好爲lOOOPa以下，更好爲l〇〇pa以下，最好爲50Pa 以下。該減壓條件之下限値並無特別限制，但就減壓裝置 性能之觀點而言，通常爲IPa。 上述步驟（2)中，使釕化合物加熱分解之溫度較好 爲100〜800°C，更好爲100〜600°C，又更好爲180~450 °C， 再更好爲200〜420°C，最好爲250〜410°C。 本發明之化學氣相沉積方法可在惰性氣體存在下與不 -13- 201137155 存在下之任一條件下進行，且’可在還原性氣體存在下與 不存在下之任一條件下進行。但’較好存在惰性氣體與還 原性氣體之任一方或二者。 該惰性氣體列舉爲例如氮氣、氬氣、氦氣等。另外， 還原性氣體可列舉爲例如氫氣、氨氣等。又本發明之化學 氣相沉積方法亦可在氧化性氣體共存下實施。此處，氧化 性氣體可列舉爲例如氧、一氧化碳、一氧化氮等^ 尤其’爲了降低成膜之釕膜中之雜質量，較好共存有 該等還原性氣體。共存有還原性氣體時，氛圍中之還原性 氣體之比例較好爲1〜100莫耳％，更好爲3〜1〇〇莫耳％。 氛圍中之氧化性氣體之比例較好爲1 0莫耳％以下，更 好爲1莫耳％以下，最好爲0.1莫耳％以下。 本發明之化學氣相沉積方法中之上述步驟（2)亦可 在加壓下、常壓下及減壓下之任一條件下進行。其中，較 好在常壓下或減壓下進行，更好在15,OOOPa以下之壓力下 實施。 本發明之釕膜形成用材料較好保存在惰性氣體之氛圍 下。至於惰性氣體列舉爲例如氮氣、氬氣、氦氣等。 如上述獲得之釕膜之純度及導電性高，可較好地使用 於例如配線電極之障壁膜、電鍍成長膜、電容電極等。 [實施例] 以下藉由實施例具體說明本發明，但本發明並不受該 等實施例之任何限制。 -14- 201137155 [合成例i]伍（三氟膦）釕（〇)之合成 使置入三氯化釕5.03g、銅10.08g之反應器抽真空’ 導入三氟隣直到成爲500atm爲止，在250°C加熱15小時。 反應結束後，將溶液冷卻至室溫後進行減壓乾燥，去除三 氣膦。在30°C、〇.〇13atm ( lOTorr)下昇華純化該所得固 體，獲得伍（三氟膦）釕（〇) 7.8〇g之白色固體。收率爲 6 0重量％。 [合成例2]伍（三乙基膦）釕（〇)之合成 將置入三氯化釕5.03g、銅10.08g、三乙基膦lOmL之 安瓶封管，在220 °C加熱24小時。反應結束後，將溶液冷 卻至室溫後，在氮氣氛圍下過濾。減壓乾燥濾液去除三乙 基膦，獲得伍（三乙基膦）釕（〇) 3.67g之白色固體。收 率爲2 2重量°/。。 [合成例3] (1，5-環辛二烯）參（三氟膦）釕（0) 之合成 將置入三氯化釕5.03g、銅l〇.〇8g、1，5-環辛二烯 50mL之反應器冷卻至-78°C後成爲真空，導入三氟膦直到 成爲400atm爲止，在180°C加熱72小時。反應結束後，將 溶液冷卻至室溫後在氮氣氛圍下過濾，減壓乾燥濾液後， 在氮氣氛圍下進行氧化鋁管柱層析（展開溶劑：二乙醚） ，濃縮所得溶液，獲得（1,5-環辛二烯）參（三氟膦）釕 -15- 201137155 (〇) 1.71g之淡黃色液體。收率爲15重量 [合成例4] (1，5_環辛二烯）參（三甲基膦）釕（0 )之合成 將置入三氯化釕5.〇3g、銅l〇.〇8g、1,5-環辛二烯 20mL、三甲基隣10mL之安瓶封管，在160°C力Π熱90小時。 反應結束後，將溶液冷卻至室溫後，在氮氣氛圍下過濾。 減壓乾燥濾液後，在氮氣氛圍下進行氧化鋁管柱層析（展 開溶劑：二乙醚），濃縮所得溶液，獲得（1，5-環辛二烯 )參（三甲基膦）釕（〇) 0.63 g之淡黃色液體。收率爲6 重量％。 [合成例5]二氫化肆（三氟膦）釕（II)之合成 使置入三氯化釕5.03g、銅l〇.〇8g之反應器抽真空， 導入3 00atm三氟膦、lOOatm氫氣，在270°C加熱15小時。 反應結束後，將溶液冷卻至室溫後進行減壓乾燥，去除三 氟鱗及氫。所得之溶液在氮氣氛圍下過濾，在室溫下以 0.0 13atm ( lOTorr )減壓蒸餾，獲得二氫化肆（三氟膦） 釕（II) 7.68g之無色透明液體。收率爲70重量。^ [合成例6] ( 1，5-辛二烯）參（三氟膦）釕（〇 )之 合成 將置入三氯化釕5.03g、銅10.08g、I，5-環辛二烯 50mL之反應器冷卻至-78 °C後抽真空，導入三氟膦直到成 -16- 201137155 爲400atm爲止，在120°C加熱100小時。反應結束後’將溶 液冷卻至室溫後在氮氣氛圍下過濾。減壓乾燥濾液後’在 氮氣氛圍下進行氧化鋁管柱層析（展開溶劑：二乙醚）， 濃縮所得溶液，獲得（1，5-環辛二烯）參（三氟膦）釕（ 〇) 1.14g之淡黃色液體。收率爲10重量％。 [合成例7](二氯）肆（三氟膦）釕（II )之合成 使置入三氯化釕5.03g、銅10.08g之反應器抽真空， 導入300atm三氟膦、lOOatm氯，在250 °C加熱15小時。反 應結束後，將溶液冷卻至室溫後進行減壓乾燥，去除三氟 膦及氯。在氮氣氛圍下過濾所得液體，在室溫下以lOTorr 減壓蒸餾，獲得（二氯）肆（三氟膦）釕（Π) 4.8 3 g之淡 黃色液體。收率爲4 1重量％。 以下實施例中，比電阻係利用Napson公司製造之探針 電阻率測定器（型號：RT-8〇/RG-80 )測定。膜厚係利用Ru ( PRS ) 1 ( L1) m ( L2) η ( 1 ) In the above formula (1), R 1 is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having a carbon number, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, preferably The halogen atom, the hydrocarbon group having 1 to 4 carbon atoms, or the halogenated hydrocarbon group having 1 to 4 carbon atoms, more preferably the halogen atom in the halogen atom R1 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably A fluorine atom or a chlorine atom is more preferably a fluorine atom. Further, the hydrocarbon group having 1 to 4 carbon atoms in R1 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a t-butyl group, preferably a methyl group or an ethyl group. , n-propyl, isopropyl, tert-butyl, more preferably methyl, ethyl fluorene, and the halogenated hydrocarbon group having 1 to 4 carbon atoms in R1 is preferably a fluorinated hydrocarbon group, a chlorinated hydrocarbon group or a brominated hydrocarbon group. More preferably, it is a fluorinated hydrocarbon group. Specific examples thereof include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, Perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2, 2,2-Trifluoroethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, 201137155 perfluoro-tert-butyl, more preferably fluoromethyl, difluoromethyl, trifluoromethyl , 2,2,2-trifluoroethyl, pentafluoroethyl. In the formula (1), L1 is a hydrogen atom or a halogen atom, preferably a hydrogen atom. When L1 is a halogen atom, the halogen atom is exemplified by a fluorine atom, a chlorine atom or a bromine atom 'iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. Further, in the formula (1), L2 is an unsaturated hydrocarbon compound having 4 to 10 carbon atoms and having at least two double bonds. Specific examples thereof include 1,3-pentadiene, 1,5-hexadiene, iota, hexadiene, 1,3-hexadiene, 2,4-hexadiene, and 3-methyl group. -1,3-pentadiene, 2-methyl-1,4-pentadiene, 1,6-heptadiene, 1,5-heptadiene, iota, 4-heptadiene, 1,7- Chain diene such as octadiene, 1,6-octadiene, 1,5-octadiene, 1,4-octadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene a cyclic diene such as 1, 4-cyclohexadiene or 1,3-cyclohexadiene. Further, in the formula (1), 1 is an integer of 1 to 5, and from the viewpoint of increasing the vapor pressure of the compound, it is preferably an integer of from 3 to 5. Further, in the formula (1), m is an integer of 〇4, and it is preferably an integer of 〇3 to 3, and more preferably an integer of 〇~2 from the viewpoint of lowering the melting point of the compound. Further, in the formula (1), η is an integer of 〇 〜 2, and from the viewpoint of forming a high-quality nail film having a high purity, it is preferably 〇 or 1, more preferably 0. Further, l + m + 2n = 5 or 6 The synthesis method of the compound represented by the above formula (1) is exemplified by including, for example, ruthenium trichloride and PR!3 in the above formula (1). -10- 201137155 Method of the step of the reaction of the compound. Further, in the above step, at least one compound selected from hydrogen, fluorine, chlorine, bromine and iodine, and the carbon number represented by L2 in the above formula (1) having at least two double bonds may be used as needed. At least one compound selected from 4 to 10 unsaturated hydrocarbon compounds is reacted. The above reaction is preferably carried out in the presence of a catalyst, and examples of the catalyst include copper, zinc and the like. The reaction temperature is not particularly limited, and is preferably from 50 to 400 ° C, more preferably from 100 to 3 50 ° C, still more preferably from 120 ° C to 300 ° C. Further, the pressure at the time of the reaction is not particularly limited, but when trifluorophosphine, hydrogen, fluorine, chlorine or the like is reacted as a gas compound under standard conditions, it is usually 10 to 1000 atmospheres (hereinafter, also referred to as "atm"). Preferably, it is 50 to 800 atmospheres, more preferably 1 to 600 atmospheres. Specific examples of the compound represented by the above formula (1) include, for example, the following compounds: 1 = 5, m = 0, n = a compound of ruthenium, which is a ruthenium (trifluorophosphine) ruthenium (〇), The valence of trichlorophosphine) ruthenium (〇), wu (trimethylphosphine) ruthenium (0), wu (triethylphosphine) ruthenium (0), etc. is 钌 钌 compound; 1 = 3,111 = 0 , 11 = 1 compound, is (7?-1,4-cyclohexane) ginseng (trifluorophosphine) ruthenium (0), (7? -1,4-cyclohexadiene) ginseng (trimethyl Phosphine) ruthenium (〇), (1,5-cyclooctadiene) ginseng (trifluorophosphine) ruthenium (0), (1,5-cyclooctadiene) ginseng (trimethylphosphine) ruthenium (0), (77-1,6-heptadiene) ginseng (trifluorophosphine) ruthenium (0), (7?-1,6-heptadiene) ginseng (trimethylphosphine) ruthenium (〇), (τ?- 1,7-octadiene) ginseng (trifluorophosphine) ruthenium (0) -11 - 201137155, (77-1,7-octadiene) ginseng (trimethylphosphine) ruthenium (〇), etc. a compound of the formula; 1 = 4' m = 2, n = 0, which is an indane (trifluoro(II), (difluoro) fluorene (trifluorophosphine) ruthenium (II), (dichlorotrifluorophosphine) )钌(II), II a ruthenium compound of ruthenium (trimethylphosphine) ruthenium (Π difluoro) ruthenium (trimethylphosphine) ruthenium (II), (dichloro) ruthenium (III) ruthenium (Π), etc.; a compound of 3, m = 3, n = 0, which is a trihydrogen (trifluoro(III), (trifluoro) gin (trifluorophosphine) ruthenium (III), etc., which is a ruthenium compound; 1 = 2 , m = 4, n = 〇 compound, tetrahydrobis(trifluoro(IV), (tetrafluoro) bis(trifluorophosphine) ruthenium (IV), (tetrachlorotrifluorophosphine) ruthenium (IV), hydrogenation (Trifluoro) guanidine (trifluorophosphine) ruthenium, dihydro(difluoro) ruthenium (trifluorophosphine) ruthenium (IV), dihydrogen) ruthenium (trifluorophosphine) ruthenium (IV), trihydrogen (fluoro) ruthenium ( A compound having a valence of 3 or more such as trifluoro(IV) or trihydro(iodo)phosphonium (trifluorophosphine) ruthenium (iv); etc. These compounds may be used singly or in combination of two or more. It is preferable to use a single compound as a ruthenium film. The ruthenium film formation method of the present invention is a method for forming the ruthenium film. The ruthenium film formation method of the present invention may be used in addition to the use of the above ruthenium film formation. As a known method, for example, an atomic phosphine such as the following may be used as a material for forming an atomic film of bis((IV)(dibromophosphine) ruthenium. Material -12-201137155 Vapor deposition method (including the following steps (1) and (2)) is carried out, and the material for forming a ruthenium film of the present invention is supplied to a substrate (for example, a substrate). The ruthenium film forming material supplied onto the substrate is thermally decomposed to form a ruthenium film on the substrate. Specifically, (1) vaporizing or evaporating the material for forming a nail film of the present invention under reduced pressure and heating, and depositing a vapor or an evaporant on a substrate (for example, a substrate), and then (2) obtaining the resultant The deposit is heated to thermally decompose to form a ruthenium film on the substrate. Further, in the above step (1), even if the material for forming a ruthenium film of the present invention is decomposed, the effects of the present invention are not impaired, and the above step (1) and the above step (2) can be simultaneously performed. The base material used herein may be a suitable material such as glass, ruthenium semiconductor, quartz, metal, metal oxide, synthetic resin, etc., but is preferably a material which can withstand the temperature at which the ruthenium compound is thermally decomposed. In the above step (1), the temperature at which the ruthenium compound is vaporized or evaporated is preferably from -100 to 35 ° C ', more preferably from -80 to 200. (:, preferably -60 to 15 〇r. In the above step (1), the pressure-reducing condition for vaporizing or evaporating the ruthenium compound is preferably not more than 100 OPa, more preferably 1 〇〇pa or less, and most preferably The lower limit of the reduced pressure condition is not particularly limited, but is usually IPa from the viewpoint of the performance of the pressure reducing device. In the above step (2), the temperature at which the cerium compound is thermally decomposed is preferably from 100 to 800. °C, more preferably 100 to 600 ° C, still more preferably 180 to 450 ° C, still more preferably 200 to 420 ° C, and most preferably 250 to 410 ° C. The chemical vapor deposition method of the present invention can be It is carried out in the presence of an inert gas under any of the conditions of the absence of -13-201137155, and can be carried out under any of the conditions of reducing gas and in the absence of it. However, it is preferred to have inert gas and reducing property. The inert gas is exemplified by, for example, nitrogen gas, argon gas, helium gas, etc. Further, the reducing gas may be, for example, hydrogen gas, ammonia gas, etc. Further, the chemical vapor deposition method of the present invention may also be The oxidizing gas is carried out in the presence of a oxidizing gas. Here, the oxidizing gas may be exemplified by, for example, oxygen. Carbon monoxide, nitrogen monoxide, etc. In particular, in order to reduce the amount of impurities in the film formed film, the reducing gas preferably coexists. When a reducing gas is present, the proportion of the reducing gas in the atmosphere is preferably 1 ~100% by mole, more preferably 3~1〇〇% by mole. The proportion of oxidizing gas in the atmosphere is preferably 10% or less, more preferably 1% by mole or less, and most preferably 0.1%. The above step (2) in the chemical vapor deposition method of the present invention may be carried out under any conditions of pressure, normal pressure and reduced pressure, wherein it is preferably under normal pressure or reduced. The pressing is carried out, and it is preferably carried out under a pressure of 1,500 OOPa. The material for forming a ruthenium film of the present invention is preferably stored under an atmosphere of an inert gas. The inert gas is exemplified by, for example, nitrogen gas, argon gas, helium gas or the like. The ruthenium film obtained as described above has high purity and conductivity, and can be preferably used for, for example, a barrier film of a wiring electrode, a plated growth film, a capacitor electrode, etc. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention It is not limited by any of the embodiments. -14- 201137155 [Synthesis Example i] Synthesis of uranium (trifluorophosphine) ruthenium (ruthenium) The reactor in which 5.03 g of antimony trichloride and 10.08 g of copper were placed was evacuated and introduced into a trifluoron to become 500 atm. The mixture was heated at 250 ° C for 15 hours. After the reaction was completed, the solution was cooled to room temperature and dried under reduced pressure to remove the tri-phosphine. The obtained solid was purified by sublimation at 30 ° C, 〇 13 m 13 atm (10 Torr) to obtain Trifluorophosphine) 〇 (〇) 7.8 〇g of a white solid. The yield was 60% by weight. [Synthesis Example 2] Synthesis of uranium (triethylphosphine) ruthenium (〇) will be placed in ruthenium trichloride 5.03g An ampule of copper 10.08 g and triethylphosphine 10 mL was sealed and heated at 220 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature and filtered under a nitrogen atmosphere. The filtrate was dried under reduced pressure to remove triethylphosphine to obtain 3.67 g of white solid (yield of triethylphosphonium). The yield is 22 weight ° /. . [Synthesis Example 3] Synthesis of (1,5-cyclooctadiene) ginseng (trifluorophosphine) ruthenium (0): 5.03 g of antimony trichloride, copper l〇.〇8 g, 1,5-cyclooctane was placed. The reactor of 50 mL of the diene was cooled to -78 ° C and then vacuumed, and trifluorophosphine was introduced until it reached 400 atm, and heated at 180 ° C for 72 hours. After completion of the reaction, the solution was cooled to room temperature, filtered under a nitrogen atmosphere, and the filtrate was dried under reduced pressure, and then subjected to alumina column chromatography (developing solvent: diethyl ether) under a nitrogen atmosphere, and the obtained solution was concentrated to obtain (1, 5-cyclooctadiene) ginseng (trifluorophosphine) 钌-15- 201137155 (〇) 1.71g of a pale yellow liquid. The yield was 15% [Synthesis Example 4] (1,5-cyclooctadiene) ginseng (trimethylphosphine) ruthenium (0) was synthesized by placing ruthenium trichloride 5. 〇 3 g, copper l 〇. 8 g, 1,5-cyclooctadiene 20 mL, trimethyl-n- 10 mL ampules were sealed and heated at 160 ° C for 90 hours. After completion of the reaction, the solution was cooled to room temperature and then filtered under a nitrogen atmosphere. The filtrate was dried under reduced pressure, and then subjected to an alumina column chromatography (developing solvent: diethyl ether) under a nitrogen atmosphere, and the obtained solution was concentrated to obtain (1,5-cyclooctadiene) ginseng (trimethylphosphine) ruthenium (〇). ) 0.63 g of pale yellow liquid. The yield was 6% by weight. [Synthesis Example 5] Synthesis of indane (trifluorophosphine) ruthenium (II) A reactor in which 5.03 g of ruthenium trichloride and 8 g of copper were placed was evacuated, and 300 atm of trifluorophosphine and 100 atm of hydrogen were introduced. Heat at 270 ° C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and dried under reduced pressure to remove trifluoroseries and hydrogen. The obtained solution was filtered under a nitrogen atmosphere, and distilled under reduced pressure at room temperature at 0.0 13 atm (10 Torr) to obtain 7.68 g of a colorless transparent liquid of indane (trifluorophosphonium) ruthenium (II). The yield was 70% by weight. ^ [Synthesis Example 6] Synthesis of (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (ruthenium) 5.03 g of antimony trichloride, 10.08 g of copper, and 50 mL of 1,5-cyclooctadiene were placed. The reactor was cooled to -78 ° C, and then evacuated, and trifluorophosphine was introduced until it was 400 atm of -16-201137155, and heated at 120 ° C for 100 hours. After the reaction was completed, the solution was cooled to room temperature and filtered under a nitrogen atmosphere. After drying the filtrate under reduced pressure, an alumina column chromatography (developing solvent: diethyl ether) was carried out under a nitrogen atmosphere, and the resulting solution was concentrated to obtain (1,5-cyclooctadiene) gin (trifluorophosphine) ruthenium (〇). 1.14g of pale yellow liquid. The yield was 10% by weight. [Synthesis Example 7] Synthesis of (dichloro)phosphonium (trifluorophosphine) ruthenium (II) A reactor in which 5.03 g of antimony trichloride and 10.08 g of copper were placed was evacuated, and 300 atm of trifluorophosphine and 100 atm of chlorine were introduced. Heat at 250 °C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and dried under reduced pressure to remove trifluorophosphine and chlorine. The resulting liquid was filtered under a nitrogen atmosphere, and distilled under reduced pressure at 10 Torr at room temperature to obtain (dichloro)phosphonium (trifluorophosphonium) ruthenium (Π) 4.8 3 g of a pale yellow liquid. The yield was 41% by weight. In the following examples, the specific resistance was measured using a probe resistivity meter (Model: RT-8?/RG-80) manufactured by Napson Corporation. Membrane thickness utilization
Philips公司製造之斜入射X射線分析裝置（型號：X’pert MRD )測定。ESCA光譜係利用日本電子公司製造之測定 器（型號：JPS80 )測定。且，有關密著性，係以JIS K- 5 400爲準，以棋盤膠帶試驗法評價，完全未發現基板與釕 膜之剝離時評價爲「〇」，發現基板與釕膜剝離時評價爲 r v „ [實施例1] (η釕膜之形成 -17- 201137155 在氮氣中將合成例1中獲得之伍（三氟膦）釕（0 ) 0.05g計量置入石英製船型容器中，且固定於石英製反應 容器中。於反應容器內之氣流下游方向側附近放置貼附熱 氧化膜之矽晶圓，在室溫下以300mL/分鐘之流量使氫氣流 入反應容器內歷時20分鐘。隨後以100m L/分鐘之流量使氫 氣流入反應容器中，接著使系統內部減壓至13Pa後，在80 °C加熱反應容器5分鐘。自船型容器產生霧氣，且在設置 於附近之石英基板上發現堆積物。霧氣發生結束後，終止 減壓，將氮氣導入系統中恢復壓力，接著以200mL/分鐘之 流量，以101.3 kPa下使氮氣（氫氣含量：3體積％)流過 ，使反應容器之溫度上升至350°C，就此保持1小時後，於 基板上獲得具有金屬光澤之膜。該膜之膜厚爲0.05// m。 測定該膜之ESCA光譜後，在280eV及284eV觀察到屬 於111!3<1軌域之峰，完全未觀察到源自其他元素之峰，可知 爲金屬釕。且該釕膜以4端子法評價比電阻之結果示於表1 〇 對於此處所形成之釕膜，利用棋盤膠帶法評價與基板 之密著性後，完全未見到基板與釕膜之剝離。 (2 )儲存安定性之試驗 進行對熱之劣化性檢討作爲儲存安定性之確認。在氮 氣氛圍下將伍（三氟膦）釕（0) lg置於l〇〇m L容量之不 銹鋼製耐壓密閉容器中予以密閉，使系統內部減壓至13 Pa 後將容器整體加熱至80t並儲存。經一個月後伍（三氟膦 -18- 201137155 )釕（〇)在外觀上仍沒有變化。 隨後，使容器恢復至室溫，以乾燥氮氣取代容器內部 後，以與上述（1 )相同要領進行成膜後，在基板上獲得 具有金屬光澤之膜。如上述（1)同樣對所得金屬釕膜之 各種物性進行評價。結果示於表1。 (3 )氣化特性之試驗 以下述試驗方法進行氣化量之測定作爲氣化特性之確 認。在乾燥氮氣氛圍之室溫下之手套箱內，將lg之伍（三 氟隣）釕（〇 )收容於100mL容量之裝置閥門之耐壓不銹 鋼製容器內並拴緊。隨後，將容器置於加熱板上，開啓閥 門，邊以80 °C加熱邊對容器內部減壓成13Pa處理5分鐘。 隨後關閉閥門後，放置冷卻3小時使容器恢復至室溫，立 即開啓上述手套箱內之閥門，使容器內之壓力恢復至常壓 。隨後開啓容器且計測殘留之試料量，計算出減壓處理時 之氣化量，氣化量爲0.85g。 另外，以與實施例1之（2)相同之要領，對儲存一個 月之伍（三氟膦）釕（0 ) 1 g之氣化特性，亦同樣計算出 氣化量，氣化量爲0.84g。結果示於表1» [實施例2 ] (Π釕膜之形成 除使用合成例2獲得之伍（三乙基膦）釕（0) 0.0 5 g 代替伍（三氟膦）釕（0 ) 0.05 g以外，餘與實施例1同樣 -19- 201137155 ，在基板上獲得具有金屬光澤之膜。如實施例1般對所得 金屬釕膜之各種物性進行評價。結果示於表1。 (2)儲存安定性之試驗 除使用合成例2獲得之伍（三乙基膦）釕（〇 ) lg代替 伍（三氟膦）釕（0 ) 1 g作爲儲存安定性之確認以外，餘 如實施例1般進行評價。結果示於表1。 (3 )氣化特性之試驗 除使用合成例2獲得之伍（三乙基膦）釕（〇) ig代替 伍（三氟膦）釕（0 ) 1 g作爲氣化特性之確認以外，餘如 實施例1般進行氣化量之測定。結果示於表1。 [實施例3] (1 )釕膜之形成 除使用合成例3獲得之（1,5 -二環辛二烯）參（三氟 膦）釕（〇) 〇.〇5g代替伍（三氟膦）釕（0) 0.05g以外， 餘如實施例1般，在基板上獲得具有金屬光澤之膜。如實 施例1般對所得金屬釕膜之各種物性進行評價。結果示於 表1。 (2)儲存安定性之試驗 除使用合成例3獲得之（1,5 -二環辛二烯）參（三氟 膦）釕（〇) lg代替伍（三氟膦）釕（0) lg作爲儲存安定 -20- 201137155 性之確認以外，餘如實施例1般進行評價。結果示於表1。 (3 )氣化特性之試驗 除使用合成例3獲得之（1，5-二環辛二烯）參（三氧 膦）釕（〇) lg代替伍（三氟膦）釕（〇) lg作爲氣化特性 之確認以外，餘如實施例1般進行氣化量之測定。結H $ 於表1。 [實施例4] (1 )釕膜之形成 除使用合成例4獲得之（1，5-二環辛二嫌）參（三甲 基膦）釕（〇 ) 〇.〇5g代替伍（三氟膦）釕（0) 〇.〇5g以外 ，餘如實施例1般，在基板上獲得具有金屬光澤之膜。如 實施例1般對所得金屬釕膜之各種物性進行評價。，結果示 於表1。 (2)儲存安定性之試驗 除使用合成例4獲得之（1,5-二環辛二嫌）參（三甲 基膦）釕（〇) lg代替伍（三氟膦）釕（〇) lg作爲儲存安 定性之確認以外’餘如實施例1般進行評價。結果示於表i (3 )氣化特性之試驗 除使用合成例4獲得之（1，5-二環辛二烯）參（三甲 -21 - 201137155 基膦）釕（〇) 1 g代替伍（三氟膦）釘（〇 性之確認以外，餘如實施例1般進行氣化 示於表1。 [實施例5] (1 )釕膜之形成 除使用合成例5獲得之二氫化肆（三 〇.〇5g代替伍（三氟膦）釕（〇) 0.05g, °C改爲反應容器爲-50°C以外，餘如實施它 獲得具有金屬光澤之膜。如實施例1般對 各種物性進行評價。結果示於表1。 (2)儲存安定性之試驗 進行劣化性之檢討作爲儲存安定性之 圍下將二氫化肆（三氟膦）釕（II) lg置 不銹鋼製耐壓密閉容器中並密閉，使系統 後將容器整體冷卻至-50 °C並儲存。經一 (三氟膦）釕（Π)在外觀上並無變化。 隨後，使容器恢復至室溫，以乾燥氮 後，以與上述（1 )相同之要領進行成膜 得具有金屬光澤之膜。如實施例1般對所 種物性進行評價，未發現變化。結果示於 (3 )氣化特性之試驗 )1 g作爲氣化特 量之測定。結果 氟膦）釕（II ) 且反應容器爲80 〖|J 1般，在基板上 所得金屬釕膜之 確認。在氮氣氛 於lOOmL容量之 內部減壓至13Pa 個月後二氫化肆 氣取代容器內部 後，在基板上獲 得金屬釕膜之各 表1。 -22- 201137155 以下述之試驗方法進行氣化量之測定作爲氣化特性之 確認。在乾燥氮氣氛圍之室溫下之手套箱內，將lg之二氫 化肆（三氟膦）釕（II )收容於lOOmL容量之裝置閥門之 耐壓不銹鋼製容器內並拴緊。隨後，將容器置於加熱板上 ，開啓閥門，且邊以- 5〇t冷卻邊對容器內部減壓至13Pa 處理5分鐘。隨後關閉閥門後，經過3小時使容器恢復至室 溫，立即開啓上述手套箱內之閥門，使容器內之壓力恢復 至常壓。隨後開啓容器且計測殘留之試料量，計算出減壓 處理時之氣化量，氣化量爲〇.98g。 另外，以與上述實施例5之（2)相同之要領，對儲存 —個月之二氫化肆（三氟膦）釕（II) lg之氣化特性，同 樣計算出氣化量，氣化量爲1 .OOg。結果示於表1。 [實施例6] (1 )釕膜之形成 除使用合成例6獲得之（1，5-辛二烯）參（三氟膦） 釕（0) 0.05g代替伍（三氟膦）釕（0) 0.05g以外，餘如 實施例1般，在基板上獲得具有金屬光澤之膜。如實施例1 般對所得金屬釕膜之各種物性進行評價。結果示於表1。 (2)儲存安定性之試驗 除使用合成例6獲得之（1，5-辛二烯）參（三氟膦） 釕（〇) lg代替伍（三氟膦）釕（〇) lg作爲儲存安定性之 確認以外，餘如實施例1般進行評價。結果示於表1。 -23- 201137155 (3 )氣化特性之試驗 除使用合成例6獲得之（1，5-辛二烯）參（三氟膦） 釕（〇) lg代替伍（三氟膦）釕（〇) lg作爲氣化特性之確 認以外，餘如實施例1般進行氣化量之測定。結果示於表1 [實施例7] (1 )釕膜之形成 除使用合成例7獲得之（二氯）肆（三氟膦）釕（II )〇.〇5g代替二氫化肆（三氟膦）釕（II ) 0.05g以外，餘 如實施例5般，在基板上獲得具有金屬光澤之膜。如實施 例5般對所得金屬釕膜之各種物性進行評價。結果示於表i (2)儲存安定性之試驗 除使用合成例7獲得之（二氯）肆（三氟膦）釕（Π )lg代替二氫化肆（三氟膦）釕（II ) lg作爲儲存安定性 之確認以外，餘如實施例5般進行評價。結果示於表 (3 )氣化特性之試驗 除使用合成例7獲得之（二氯）肆（三氟膦）釕（II )lg代替二氫化肆（三氟膦）釕（Π) lg作爲氣化特性之 確認以外，餘如實施例5般進行氣化量之測定。結果示於 -24- 201137155 表1。 [表1] 儲存溫度 與時間 外觀上之變化 氣化量 (g) 比電阻 (μ Ω · c) 密著性 實施例1 - _ 0.85 35 〇 8(TC—個月 無變化 0.84 36 〇 實施例2 _ 0.81 56 〇 80°C-個月 無變化 0.79 58 〇 實施例3 _ 一 0.86 430 〇 80°C—個月 無變化 0.85 440 〇 實施例4 _ - 0.82 490 〇 80°C—個月 無變化 0.81 479 〇 實施例5 . 0.98 26 〇 -50°C—個月 無變化 1.00 24 〇 實施例6 _ 0.88 380 〇 80t—個月 無變化 0.85 367 〇 實施例7 - _ 0.81 88 〇 -50°C—個月 無變化 0.81 90 〇 -25-Measured by an oblique incident X-ray analyzer (model: X'pert MRD) manufactured by Philips. The ESCA spectrum was measured using a measuring instrument (Model: JPS80) manufactured by JEOL. Further, regarding the adhesion, the JIS K-5400 was used as the standard, and the board tape test method was used for evaluation. When the peeling of the substrate and the ruthenium film was not found at all, it was evaluated as "〇", and it was found that the substrate and the ruthenium film were peeled off as rv. „ [Example 1] (Formation of η钌 film-17- 201137155) The amount of (trifluorophosphine) 钌(0) 0.05 g obtained in Synthesis Example 1 was placed in a quartz ship type container and fixed in a nitrogen atmosphere. In a quartz reaction vessel, a crucible wafer to which a thermal oxide film is attached is placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and hydrogen gas is introduced into the reaction vessel at a flow rate of 300 mL/min at room temperature for 20 minutes. The flow rate of L/min was such that hydrogen gas was flowed into the reaction vessel, and then the inside of the system was depressurized to 13 Pa, and then the reaction vessel was heated at 80 ° C for 5 minutes. Mist was generated from the ship type container, and deposits were found on the quartz substrate disposed nearby. After the completion of the mist, the pressure reduction was terminated, and nitrogen gas was introduced into the system to restore the pressure, and then nitrogen gas (hydrogen content: 3 vol%) was flowed at 101.3 kPa at a flow rate of 200 mL/min to raise the temperature of the reaction vessel. After maintaining for 1 hour at 350 ° C, a film having a metallic luster was obtained on the substrate. The film thickness of the film was 0.05 / / m. After measuring the ESCA spectrum of the film, it was observed at 280 eV and 284 eV belonging to 111! 3 < In the peak of the 1 orbital domain, the peak derived from other elements was not observed at all, and it was found to be a metal ruthenium. The results of the specific resistance of the ruthenium film evaluated by the 4-terminal method are shown in Table 1. For the ruthenium film formed here, use After the checkerboard tape method evaluated the adhesion to the substrate, no peeling of the substrate and the ruthenium film was observed at all. (2) Test for storage stability The heat deterioration test was confirmed as storage stability. Under nitrogen atmosphere (Trifluorophosphine) 钌 (0) lg is sealed in a stainless steel pressure-resistant closed container of l〇〇m L capacity, and the inside of the system is decompressed to 13 Pa, and the whole container is heated to 80 t and stored. After the month, (trifluorophosphine-18-201137155) 钌(〇) still has no change in appearance. Subsequently, the container is returned to room temperature, and the inside of the container is replaced with dry nitrogen, and then the same method as (1) above is carried out. After the film, the metal light is obtained on the substrate The physical properties of the obtained metal ruthenium film were evaluated in the same manner as in the above (1). The results are shown in Table 1. (3) Test for gasification characteristics The gasification amount was measured by the following test method as confirmation of gasification characteristics. In a glove box at room temperature under a dry nitrogen atmosphere, lg (trifluoro) ruthenium (〇) is contained in a pressure-resistant stainless steel container of a 100 mL capacity device valve and tightened. Subsequently, the container is placed On the hot plate, open the valve and depressurize the inside of the container to 13 Pa for 5 minutes while heating at 80 ° C. Then close the valve, let it cool for 3 hours to return the container to room temperature, and immediately open the valve in the glove box. , the pressure inside the container is restored to normal pressure. Subsequently, the container was opened and the amount of the remaining sample was measured, and the amount of vaporization at the time of pressure reduction treatment was calculated, and the amount of vaporization was 0.85 g. Further, in the same manner as in the case of (2) of Example 1, the gasification amount was also calculated for the gasification characteristics of 1 g of trifluorophosphine (0) 1 g, and the gasification amount was 0.84 g. . The results are shown in Table 1» [Example 2] (Formation of ruthenium film except for the use of Synthesis Example 2 (Triethylphosphine) 钌(0) 0.0 5 g instead of urethane (trifluorophosphine) 钌 (0) 0.05 In the same manner as in Example 1, the film having a metallic luster was obtained on the substrate in the same manner as in Example 1. The physical properties of the obtained metal tantalum film were evaluated as in Example 1. The results are shown in Table 1. (2) Storage The stability test was the same as in Example 1 except that the (triethylphosphine) ruthenium (〇) lg obtained in Synthesis Example 2 was used instead of chlorotrifluorophosphine (0) 1 g as the storage stability. The results are shown in Table 1. (3) The gasification characteristics were tested except that the (triethylphosphine) ruthenium (〇) ig obtained in Synthesis Example 2 was used instead of uranium (trifluorophosphine) ruthenium (0) 1 g. The gasification amount was measured in the same manner as in Example 1. The results are shown in Table 1. [Example 3] (1) The formation of the ruthenium film was obtained by using the synthesis example 3 (1, 5 - Dicyclooctadiene) ginseng (trifluorophosphine) ruthenium (〇) 〇. 〇 5g instead of (trifluorophosphine) ruthenium (0) 0.05g, as in Example 1, on the substrate A film having a metallic luster was obtained. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1. (2) The test for storage stability was obtained by using Synthesis Example 3 (1, 5 - 2) Cyclooctadiene) ginseng (trifluorophosphine) ruthenium (〇) lg instead of (trifluorophosphine) ruthenium (0) lg was evaluated as in the case of storage stability -20-201137155. It is shown in Table 1. (3) Test of gasification characteristics In addition to the (1,5-bicyclooctadiene) ginseng (trisphosphine) ruthenium (〇) lg obtained by the synthesis example 3, lg (trifluorophosphine) 钌(〇) lg was measured for vaporization amount as in Example 1 except that the gasification characteristics were confirmed. The knot H$ is shown in Table 1. [Example 4] (1) Formation of ruthenium film was obtained by using Synthesis Example 4. (1,5-bicyclooctane) ginseng (trimethylphosphine) ruthenium (〇) 〇.〇5g instead of wu (trifluorophosphine) 钌(0) 〇.〇5g, the remainder is as in the case of Example 1. A film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1. (2) Test for storage stability In addition to the (1,5-bicyclooctane) ginseng (trimethylphosphine) ruthenium (〇) lg obtained in the synthesis example 4, the lg (trifluorophosphine) ruthenium (〇) lg was used as the confirmation of storage stability. The evaluation was carried out in the same manner as in Example 1. The results are shown in Table i (3) Gasification characteristics except the (1,5-bicyclooctadiene) ginseng (Trimethyl-21 - 201137155 phosphine) obtained in Synthesis Example 4.钌(〇) 1 g was substituted for the urethane (trifluorophosphine) nail (the gasification was carried out as in Example 1 except that the oxime was confirmed). [Example 5] (1) Formation of ruthenium film In addition to the use of the indane obtained in Synthesis Example 5 (3 〇. 〇 5 g instead of urethane (trifluorophosphine) ruthenium (〇) 0.05 g, °C was changed to a reaction vessel - Except for 50 ° C, it was obtained by obtaining a film having a metallic luster. Various physical properties were evaluated as in Example 1. The results are shown in Table 1. (2) Storage stability test Review of deterioration as storage stability The indane (trifluorophosphine) ruthenium (II) lg was placed in a pressure-resistant closed container made of stainless steel and sealed, and the whole of the container was cooled to -50 ° C and stored. After the system (monotrifluorophosphine)钌(Π) does not change in appearance. Subsequently, the container is returned to room temperature to dry the nitrogen, and a film having a metallic luster is formed in the same manner as in the above (1). The physical properties were evaluated and no change was found. The results are shown in (3) Test of gasification characteristics) 1 g as a gasification amount. Results Fluorophosphine) ruthenium (II) and the reaction vessel was 80 〖|J 1 , and the metal ruthenium film obtained on the substrate was confirmed. After the internal pressure was reduced to 13 Pa hr in a nitrogen atmosphere at a pressure of 13 Pa after the inside of the vessel, the metal ruthenium film was obtained on the substrate. -22- 201137155 The gasification amount was measured by the following test method as confirmation of gasification characteristics. In a glove box at room temperature under a dry nitrogen atmosphere, lg of ruthenium dihydrogen hydride (trifluorophosphine) ruthenium (II) was placed in a pressure-resistant stainless steel container of a 100 mL-capacity device valve and tightened. Subsequently, the container was placed on a hot plate, the valve was opened, and the inside of the container was depressurized to 13 Pa for 5 minutes while cooling with -5 Torr. After closing the valve, the container was returned to the room temperature after 3 hours, and the valve in the glove box was immediately opened to restore the pressure in the container to normal pressure. Subsequently, the vessel was opened and the amount of the remaining sample was measured, and the amount of gasification at the time of pressure reduction treatment was calculated, and the amount of vaporization was 〇.98 g. Further, in the same manner as in the above (2) of the fifth embodiment, the gasification amount of the storage-month-old hydrazine (trifluorophosphine) ruthenium (II) lg was also calculated, and the gasification amount was calculated. 1 .OOg. The results are shown in Table 1. [Example 6] (1) Formation of ruthenium film (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (0) 0.05 g instead of (trifluorophosphine) ruthenium (0) Except for 0.05 g, as in Example 1, a film having a metallic luster was obtained on the substrate. The various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1. (2) Storage stability test except that (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (〇) obtained by using the synthesis example 6 was used instead of uranium (trifluorophosphine) ruthenium (〇) lg as storage stability. Except for the confirmation of the nature, the evaluation was carried out as in Example 1. The results are shown in Table 1. -23- 201137155 (3) Test of gasification characteristics In addition to the (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (〇) obtained by the synthesis of Example 6, lg instead of uranium (trifluorophosphine) ruthenium (〇) The lg was measured as the gasification amount in the same manner as in Example 1 except that the gasification characteristics were confirmed. The results are shown in Table 1. [Example 7] (1) Formation of ruthenium film In addition to the use of (dichloro) ruthenium (trifluorophosphine) ruthenium (II) 〇. 〇 5 g obtained in place of indane (trifluorophosphine)钌(II) Other than 0.05 g, as in Example 5, a film having a metallic luster was obtained on the substrate. The physical properties of the obtained metal ruthenium film were evaluated as in Example 5. The results are shown in Table i (2) Test for storage stability except that (dichloro)phosphonium (trifluorophosphine) ruthenium (Π) lg obtained in Synthesis Example 7 was used instead of indane (trifluorophosphine) ruthenium (II) lg as Except for the confirmation of storage stability, the evaluation was carried out as in Example 5. The results are shown in Table (3) Test of gasification characteristics except that (dichloro)phosphonium (trifluorophosphine) ruthenium (II) lg obtained in Synthesis Example 7 was used instead of indane (trifluorophosphine) ruthenium (Π) lg as a gas. The amount of gasification was measured as in Example 5 except for the confirmation of the chemical properties. The results are shown in Table -24- 201137155. [Table 1] Change in storage temperature and time appearance Gasification amount (g) Specific resistance (μ Ω · c) Adhesion Example 1 - _ 0.85 35 〇 8 (TC - month no change 0.84 36 〇 Example 2 _ 0.81 56 〇80°C-month no change 0.79 58 〇Example 3 _ A 0.86 430 〇80°C-month no change 0.85 440 〇Example 4 _ - 0.82 490 〇80°C-month Change 0.81 479 〇Example 5. 0.98 26 〇-50°C-month no change 1.00 24 〇Example 6 _ 0.88 380 〇80t-month no change 0.85 367 〇Example 7 - _ 0.81 88 〇-50° C-month no change 0.81 90 〇-25-