TW201815809A - 二氮雜二烯基化合物、薄膜形成用原料及薄膜之製造方法 - Google Patents
二氮雜二烯基化合物、薄膜形成用原料及薄膜之製造方法 Download PDFInfo
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- TW201815809A TW201815809A TW106123411A TW106123411A TW201815809A TW 201815809 A TW201815809 A TW 201815809A TW 106123411 A TW106123411 A TW 106123411A TW 106123411 A TW106123411 A TW 106123411A TW 201815809 A TW201815809 A TW 201815809A
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- thin film
- raw material
- compound
- film
- titanium
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 80
- 239000002994 raw material Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 150000002815 nickel Chemical group 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
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- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 9
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- 239000002243 precursor Substances 0.000 description 43
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- 239000012071 phase Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- 229940120731 pyruvaldehyde Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
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Abstract
一種二氮雜二烯基化合物,其係以下述通式(I)表示:上述通式(I)中,R1
係表示碳數1~6之直鏈或分支狀之烷基,M係表示鎳原子或錳原子。特別是,上述通式(I)中,R1
為甲基之化合物係蒸氣壓為高,熱分解開始溫度為高,故適宜為利用CVD法或ALD法之薄膜形成用原料。
Description
[0001] 本發明係關於一種新穎的二氮雜二烯基化合物、含有該化合物而成之薄膜形成用原料及使用該薄膜形成用原料之薄膜之製造方法。
[0002] 包含金屬元素之薄膜材料係示出電特性及光學特性,故應用於各種之用途。例如,鎳及含有鎳之薄膜係主要可使用於電阻膜、阻隔膜等之電子零件之零件、磁性膜等之記錄媒體用之零件,或電極等之薄膜太陽能電池用零件等。 [0003] 作為上述薄膜之製造法,可舉例為濺鍍法、離子鍍敷法、塗佈熱分解法,或溶凝膠法等之MOD法、CVD法、原子層沈積法(atomic layer deposition) (以下,有時亦記載為ALD法),所得之薄膜之品質為良好,故主要使用於CVD法或ALD法。 [0004] 作為可使用於化學氣相成長法之金屬供應源大多被報告出各式各樣的原料,例如,專利文獻1中,揭示出作為利用ALD法之薄膜形成用原料可使用之二氮雜二烯基錯合物。再者,專利文獻2中,揭示出可使用於化學蒸鍍法或原子層蒸鍍法之二氮雜二烯系金屬化合物。專利文獻1及專利文獻2中,對於本發明之二氮雜二烯基化合物無具體的記載。 [先前技術文獻] [專利文獻] [0005] [專利文獻1] 美國專利申請公開第2013/0164456號說明書 [專利文獻2] 日本特表2013-545755號公報
[發明所欲解決之課題] [0006] 使化學氣相成長用原料等氣化而於基材表面形成含有金屬之薄膜時,可形成蒸氣壓為高、無自燃性、高品質的薄膜之化學氣相成長用原料為適宜。為了形成更高品質的薄膜,必須使用ALD法進行200℃以上之加熱,故可適用於ALD法,且求得蒸氣壓為高、無自燃性、具有200℃以上之熱分解開始溫度之化學氣相成長用原料。所謂上述高品質的薄膜係意指膜中之殘留含碳量為少者。 [用以解決課題之手段] [0007] 本發明人等重複檢討之結果,發現特定之二氮雜二烯基化合物可解決上述課題,因而完成本發明。 [0008] 本發明係提供以下述通式(I)表示之二氮雜二烯基化合物。 [0009][0010] (式中,R1
係表示碳數1~6之直鏈或分支狀之烷基、M係表示鎳原子或錳原子)。 [0011] 再者,本發明係提供含有以上述通式(I)表示之二氮雜二烯基化合物而成之薄膜形成用原料。 [0012] 更進一步,本發明係提供一種薄膜之製造方法,其係將含有使上述薄膜形成用原料氣化而得之二氮雜二烯基化合物的蒸氣,導入設置有基體的成膜腔室內,使該二氮雜二烯基化合物分解及/或使其進行化學反應而於該基體之表面形成含有選自鎳原子及錳原子中至少1種之原子的薄膜。 [發明之效果] [0013] 依據本發明,可製得蒸氣壓為高、無自燃性、熱分解開始溫度為非常高的二氮雜二烯基化合物。該二氮雜二烯基化合物係特別適合作為利用CVD法或ALD法之薄膜形成用原料。含有該二氮雜二烯基化合物而成之薄膜形成用原料係藉由CVD法或ALD法,可形成膜中之殘留含碳量少的高品質的薄膜。其中,本發明之二氮雜二烯基化合物係與氫之反應性為特別良好,故含有該二氮雜二烯基化合物而成之薄膜形成用原料係可藉由ALD法形成非常高品質的金屬鎳薄膜。
[用以實施本發明之最佳形態] [0015] 本發明之二氮雜二烯基化合物係以上述通式(I)表示者,可較佳地作為具有CVD法等之氣化步驟之薄膜製造方法之前驅物者,亦可使用ALD法形成薄膜。 [0016] 本發明之上述通式(I)中,R1
係表示碳數1~6之直鏈或分支狀之烷基,M係表示鎳原子或錳原子。 [0017] 作為以上述R1
表示之碳數1~6之直鏈或分支狀之烷基係可舉例甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基及己基等。 [0018] 上述通式(I)中,R1
為甲基之化合物係作為使用蒸氣壓為高、熱分解開始溫度為高,利用CVD法或ALD法之薄膜形成用原料時,可製得高品質的薄膜,故特別佳。利用不伴隨氣化步驟之MOD法之薄膜之製造方法時,R1
係對於所使用之溶劑之溶解性,可依據薄膜形成反應等適當選擇。 [0019] 作為以通式(I)表示之二氮雜二烯基化合物之較佳具體例以例如舉例為下述化合物No.1~No.12表示之化合物。尚,下述化合物No.1~No.12中,「Me」表示甲基,「Et」表示乙基,「Pr」表示丙基,「iPr」表示異丙基,「sBu」表示第二丁基、「tBu」表示第三丁基。 [0020][0021][0022] 本發明之二氮雜二烯基化合物係依據該製造方法但並不特別地限制,應用周知之反應而製造。例如,製造鎳之二氮雜二烯基化合物時,例如,可舉例將鎳之鹵化物、硝酸鹽等之無機鹽或該水合物,與對應之二氮雜二烯化合物,於鈉、鋰、氫化鈉、鈉胺、氫氧化鈉、甲醇鈉、氨、胺等之鹼基之存在下反應之方法、鎳之鹵化物、硝酸鹽等之無機鹽或該水合物,與對應之二氮雜二烯化合物之鈉錯合物、鋰錯合物、鉀錯合物等反應之方法等。 尚,於此使用之二氮雜二烯化合物係依據該製造方法但並不特別限定,可藉由應用周知之反應製造。例如,使烷基胺與烷基乙二醛於三氯甲烷等之溶劑中反應者以適切的溶劑萃取,藉由脫水處理製得之方法。 [0023] 所謂本發明之薄膜形成用原料係將以上述說明之本發明之二氮雜二烯基化合物作為薄膜之前驅物者,且該形態可依據該薄膜形成用原料所適用之製造製程而相異。例如,製造僅包含選自鎳及錳所成之群中至少1種之金屬的薄膜時,本發明之薄膜形成用原料不含上述二氮雜二烯基化合物以外之金屬化合物及半金屬化合物。另一方面,製造包含2種類以上之金屬及/或半金屬之薄膜時,除了上述二氮雜二烯基化合物以外,本發明之薄膜形成用原料含有包含所期望之金屬的化合物及/或包含半金屬之化合物(以下亦稱為「其他前驅物」)。本發明之薄膜形成用原料如後述,亦可進一步含有有機溶劑及/或親核性試藥。本發明之薄膜形成用原料如上述說明,由於適用於以前驅物之二氮雜二烯基化合物的物性為CVD法、ALD法,故特別作為化學氣相成長用原料(以下亦稱為「CVD用原料」)有用。 [0024] 本發明之薄膜形成用原料為化學氣相成長用原料之時,該形態可依據所使用的CVD法之輸送供給方法等方法而適當選擇。 [0025] 作為上述之輸送供給方法,藉由將CVD用原料於儲存該原料之容器(以下有時亦簡單記載為「原料容器」)中加熱及/或減壓而氣化為蒸氣,將該蒸氣與根據需要使用之氬、氮、氦等之載氣一起導入設置基體之成膜腔室內(以下有時亦記載為「堆積反應部」)之氣體輸送法、將CVD用原料以液體或溶液狀態輸送至氣化室,於氣化室藉由加熱及/或減壓而氣化為蒸氣,將該蒸氣導入成膜腔室內之液體輸送法。氣體輸送法時,以上述通式(I)表示之二氮雜二烯基化合物本身可作為CVD用原料。液體輸送法之情況,可將以上述通式(I)表示之二氮雜二烯基化合物本身或該化合物溶於有機溶劑中之溶液作為CVD用原料。該等之CVD用原料亦可進一部包含其他前驅物或親核性試藥。 [0026] 又,於多成分系之CVD法中,有使CVD用原料各成分獨立氣化、供給之方法(以下有時亦記載為「單一源法」)與使多成分原料預先以期望組成混合之混合原料氣化、供給之方法(以下有時亦記載為「混合源法」)。混合源法之情況,可將本發明之二氮雜二烯基化合物與其他前驅物之混合物或者將該混合物溶於有機溶劑之混合溶液作為CVD用原料。該混合物或混合溶液亦可進一步包含親核性試藥等。 [0027] 作為上述有機溶劑並未特別限制,可使用周知之一般有機溶劑。作為該有機溶劑可舉例為例如乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等之乙酸酯類;四氫呋喃、四氫吡喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二丁醚、二噁烷等之醚類;甲基丁基酮、甲基異丁基酮、乙基丁基酮、二丙基酮、二異丁基酮、甲基戊基酮、環己酮、甲基環己酮等之酮類;己烷、環己烷、甲基環己烷、二甲基環己烷、乙基環己烷、庚烷、辛烷、甲苯、二甲苯等之烴類;1-氰基丙烷、1-氰基丁烷、1-氰基己烷、氰基環己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基環己烷、1,4-二氰基苯等之具有氰基之烴類;吡啶、二甲基吡啶(lutidine)等。該等之有機溶劑可根據溶質之溶解性、使用溫度與沸點、起火點之關係等而單獨或混合兩種類以上之使用。使用該等之有機溶劑時,將前驅物溶於有機溶劑之溶液的CVD用原料中之前驅物全體量0.01~2.0莫耳/升為佳,特佳為0.05~1.0莫耳/升。所謂前驅物全體量,於本發明之薄膜形成用原料不含本發明之二氮雜二烯基化合物以外之金屬化合物及半金屬化合物時,為本發明之二氮雜二烯基化合物的量,於本發明之薄膜形成用原料含有除了包含該二氮雜二烯基化合物以外之其他之金屬的化合物及或包含半金屬的化合物(其他前驅物)時,為本發明之二氮雜二烯基化合物及其他前驅物之合計量。 [0028] 且,於多成分系之CVD法時,作為與本發明之二氮雜二烯基化合物一起使用之其他前驅物並未特別限制,可使用於CVD原料中所用之周知一般前驅物。 [0029] 作為上述之其他之前驅物係可舉例選擇自將氫化物、氫氧化物、鹵化物、疊氮化物、烷基、烯基、環烷基、芳基、炔基、胺基、二烷基胺基烷基、單烷基胺基、二烷基胺基、二胺、二(矽基-烷基)胺基、二(烷基-矽基)胺基、二矽基胺基、烷氧基、烷氧基烷基、醯肼、磷化物、腈、二烷基胺基烷氧基、烷氧基烷基二烷基胺基、矽烷氧基、二酮基、環戊二烯基、矽基、吡唑特(pyrazolate)、胍酸酯(guanidinate)、磷胍酸酯、脒基(amidinate)、酮醯亞胺酯、二酮亞胺酸酯、羰基及磷脒酸酯(phosphorothioate)作為配位基所具有之化合物所成之群之一種類或二種類以上之矽或金屬之化合物。 [0030] 作為前驅物之金屬種,可舉例為鎂、鈣、鍶、鋇 鐳、鈧、釔、鈦、鋯、鉿、釩、鈮、鉭、鉻、鉬、鎢、鐵、鋨、鈷、銠、銥、鈀、鉑、銅、銀、金、鋅、鎘、鋁、鎵、銦、鍺、錫、鉛、銻、鉍、鑭、鈰、鐠、釹、鉅、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿。 [0031] 上述之其他之前驅物為本技術領域中習知者,其製造方法亦為習知。若舉製造方法之一例,在例如使用醇化合物作為有機配位基時,藉由使如前述之金屬無機鹽或其水合物與該醇化合物之鹼金屬烷氧化物反應,可製造前驅物。於此,金屬之無機鹽或其水合物可舉例為金屬之鹵化物、硝酸鹽等,作為鹼金屬烷氧化物可舉例為烷氧化鈉、烷氧化鋰、烷氧化鉀等。 [0032] 上述之其他之前驅物,於單一源法時,本發明之二氮雜二烯基化合物與熱及/或氧化分解行為類似之化合物為佳,於混合源法時,除了熱及/或氧化分解行為類似以外,混合時不引起化學反應等之變質者為較佳。 [0033] 上述之其他之前驅物中,作為包含鈦、鋯或鉿之前驅物係可舉例以下述式(II-1)~(II-5)表示之化合物。 [0034][0035] (式中,M1
係表示鈦、鋯或鉿,Ra
及Rb
係各自獨立地表示可以鹵原子取代、可於鏈中包含氧原子之碳數1~20之烷基,Rc
係表示碳數1~8之烷基,Rd
係表示碳數2~18之可分支之伸烷基,Re
及Rf
係各自獨立地表示氫原子或碳數1~3之烷基,Rg
、Rh
、Rk
及Rj
係各自獨立表示氫原子或碳數1~4之烷基,p係表示0~4之整數,q係表示0或2,r係表示0~3之整數,s係表示0~4之整數,t係表示1~4之整數)。 [0036] 上述式(II-1)~(II-5)中,作為以Ra
及Rb
表示之可以鹵原子取代、可於鏈中包含氧原子之碳數1~20之烷基係可舉例甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、新戊基、第三戊基、己基、環己基、1-甲基環己基、庚基、3-庚基、異庚基、第三庚基、n-辛基、異辛基、第三辛基、2-乙基己基、三氟甲基、全氟己基、2-甲氧基乙基、2-乙氧基乙基、2-丁氧基乙基、2-(2-甲氧基乙氧基)乙基、1-甲氧基-1,1-二甲基甲基、2-甲氧基-1,1-二甲基乙基、2-乙氧基-1,1-二甲基乙基、2-異丙氧基-1,1-二甲基乙基、2-丁氧基-1,1-二甲基乙基、2-(2-甲氧基乙氧基)-1,1-二甲基乙基等。再者,作為以Rc
表示之碳數1~8之烷基係可舉例甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、新戊基、第三戊基、己基、1-乙基戊基、環己基、1-甲基環己基、庚基、異庚基、第三庚基、n-辛基、異辛基、第三辛基、2-乙基己基等。再者,所謂以Rd
表示之碳數2~18之可分支之伸烷基係可藉由二醇賦予之基,作為該二醇係可舉例如1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、2,4-己二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2,2-二乙基-1,3-丁二醇、2-乙基-2-丁基-1,3-丙二醇、2,4-戊二醇、2-甲基-1,3-丙二醇、1-甲基-2,4-戊二醇等。再者,作為以Re
及Rf
表示碳數1~3之烷基係可舉例甲基、乙基、丙基、2-丙基等。作為以Rg
、Rh
、Rj
及Rk
表示之碳數1~4之烷基係可舉例甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基等。 [0037] 具體而言之,包含鈦之前驅物係可舉例如四(乙氧基)鈦基、四(2-丙氧基)鈦基、四(丁氧基)鈦基、四(第二丁氧基)鈦基、四(異丁氧基)鈦基、四(第三丁氧基)鈦基、四(第三戊基)鈦基、四(1-甲氧基-2-甲基-2-丙氧基)鈦基等之四烷氧基鈦基類;四(戊烷-2,4-二酮根基(dionate))鈦基、(2,6-二甲基庚烷-3,5-二酮根基)鈦基、四(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基等之四β-二酮基鈦基類;雙(甲氧基)雙(戊烷-2,4-二酮根基)鈦基、雙(乙氧基)雙(戊烷-2,4-二酮根基)鈦基、雙(第三丁氧基)雙(戊烷-2,4-二酮根基)鈦基、雙(甲氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基、雙(乙氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基、雙(2-丙氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基、雙(第三丁氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基、雙(第三戊氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基、雙(甲氧基)雙(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基、雙(乙氧基)雙(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基、雙(2-丙氧基)雙(2,6,6,6-四甲基庚烷-3,5-二酮根基)鈦基、雙(第三丁氧基)雙(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基、雙(第三戊氧基)雙(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基等之雙(烷氧基)雙(β二酮基)鈦基類;(2-甲基戊烷二氧基)雙(2,2,6,6-四甲基庚烷-3,5-二酮根基)鈦基、(2-甲基戊烷二氧基)雙(2,6-二甲基庚烷-3,5-二酮根基)鈦基等之乙醛醯基雙(β二酮基)鈦基類;(甲基環戊二烯基)三(二甲基胺基)鈦基、(乙基環戊二烯基)三(二甲基胺基)鈦基、(環戊二烯基)三(二甲基胺基)鈦基、(甲基環戊二烯基)三(乙基甲基胺基)鈦基、(乙基環戊二烯基)三(乙基甲基胺基)鈦基、(環戊二烯基)三(乙基甲基胺基)鈦基、(甲基環戊二烯基)三(二乙基胺基)鈦基、(乙基環戊二烯基)三(二乙基胺基)鈦基、(環戊二烯基)三(二乙基胺基)鈦基等之(環戊二烯基)三(二烷基胺基)鈦基類;(環戊二烯基)三(甲氧基)鈦基、(甲基環戊二烯基)三(甲氧基)鈦基、(乙基環戊二烯基)三(甲氧基)鈦基、(丙基環戊二烯基)三(甲氧基)鈦基、(異丙基環戊二烯基)三(甲氧基)鈦基、(丁基環戊二烯基)三(甲氧基)鈦基、(異丁基環戊二烯基)三(甲氧基)鈦基、第三丁基環戊二烯基)三(甲氧基)鈦基、(五甲基環戊二烯基)三(甲氧基)鈦基等之(環戊二烯基)三(烷氧基)鈦基類等。作為包含鋯之前驅物或包含鉿之前驅物係可舉例如將包含上述鈦之前驅物例示之化合物中之鈦置換為鋯或鉿之化合物。 [0038] 作為包含烯土類元素之前驅物係可舉例如以下述式(III-1)~(III~3)表示之化合物。 [0039][0040] (式中,M2
係表示烯土類原子,Ra
及Rb
係各自獨立表示可以鹵原子取代、可於鏈中包含氧原子之碳數1~20之烷基,Rc
係表示碳數1~8之烷基,Re
及Rf
係各自獨立表示氫原子或碳數1~3之烷基,Rg
及Rj
係各自獨立表示碳數1~4之烷基,p’係表示0~3之整數,r’係表示0~2之整數)。 [0041] 包含上述之烯土類元素之前驅物中,作為以M2
表示之烯土類原子係可舉例如鈧、釔、鑭、鈰、鐠、釹、鉅、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿、鎦。作為以Ra
、Rb
、Rc
、Re
、Rf
、Rg
及Rj
表示之基係可舉例如包含前述之鈦之以前驅物例示之基。 [0042] 再者,本發明之薄膜形成用原料,根據需要,為了賦予本發明之二氮雜二烯基化合物及其他之前驅物之安定性,亦可含有親核性試藥。作為該親核性試藥舉例為甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚等之乙二醇醚類,18-冠狀醚-6、二環己基-18-冠狀醚-6、24-冠狀醚-8、二環己基-24-冠狀醚-8、二苯并-24-冠狀醚-8等之冠狀醚類,乙二胺、N,N’-四甲基乙二胺、二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六胺、1,1,4,7,7-五甲基二伸乙三胺、1,1,4,7,10,10-六甲基三伸乙四胺、三乙氧基三伸乙胺等之聚胺類、四氮雜環十四烷(cyclam)、四氮雜環十二烷(cyclen)等之環狀聚胺類、吡啶、吡咯啶、哌啶、嗎啉、N-甲基吡咯啶、N-甲基哌啶、N-甲基嗎啉、四氫呋喃、四氫吡喃、1,4-二噁烷、噁唑、噻唑、氧雜硫雜環戊烷(oxathiolane)等之雜環化合物類、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸-2-甲氧基乙酯等之β-酮酯類或乙醯丙酮、2,4-己二酮、2,4-庚二酮、3,5-庚二酮、二特戊醯基甲烷等之β-二酮類。該等親核性試藥之使用量,對於前驅物全體之量1莫耳,0.1莫耳~10莫耳之範圍為佳,1~4莫耳為更佳。 [0043] 在本發明之薄膜形成用原料中極力不包含構成其之成分以外之雜質金屬元素分、雜質氯等之雜質鹵素分及雜質有機分。雜質金屬元素分之每元素100ppb以下為佳,10ppb以下為更佳,總量計係1ppm以下為佳,100ppb以下為更佳。尤其,使用作為LSI之閘極絕緣膜、閘極膜、障壁層時,必須減少對所得薄膜之電特性有影響之鹼金屬元素及鹼土類金屬元素之含量。雜質鹵素分100ppm以下為佳,10ppm以下為更佳,1ppm以下為最佳。雜質有機分總量計係500ppm以下為佳,50ppm以下為更佳,10ppm以下為最佳。又,由於水分係化學氣相成長用原料中之顆粒發生或薄膜形成中之顆粒發生之原因,故前驅物、有機溶劑及親核性試藥中,為了減低各自之水分,使用時較佳預先儘可能去除水分。前驅物、有機溶劑及親核性試藥各水分量10ppm以下為佳,1ppm以下為更佳。 [0044] 又,本發明之薄膜形成用原料,為了減低或防止所形成之薄膜的顆粒污染,較好極力不包含顆粒。具體而言,於液相之藉由光散射式液中粒子檢測器之顆粒測定中,大於0.3μm之粒子數於液相1ml中100個以下為佳,大於0.2μm之粒子數於液相1ml中1000個以下為更佳,大於0.2μm之粒子數於液相1ml中100個以下為最佳。 [0045] 作為使用本發明之薄膜形成用原料製造薄膜之本發明之薄膜之製造方法,係將本發明之薄膜形成用原料氣化之蒸氣及根據需要使用之反應性氣體導入設置有基體之成膜腔室內,接者,使前驅物於基體上分解及/或化學反應,於基體表面成長並堆積含金屬之薄膜的CVD法者。原料之輸送供給方法、堆積方法、製造條件、製造裝置等並未特別受到限制,可使用周知之一般條件及方法。 [0046] 作為上述根據需要使用之反應性氣體,例如作為氧化性者舉例為氧、臭氧、二氧化氮、一氧化氮、水蒸氣、過氧化氫、甲酸、乙酸、乙酸酐等,作為還原性者舉例為氫,且作為製造氮化物者,舉例為單烷胺、二烷胺、三烷胺、伸烷二胺等之有機胺化合物、聯胺、氨等,該等可使用一種或兩種以上。其中,本發明之二氮雜二烯基化合物係與氫之反應性為特別良好,故使用氫作為反應性氣體與藉由ALD法,可形成非常高品質的金屬鎳薄膜。 [0047] 且,作為上述輸送供給方法,舉例為前述之氣體輸送法、液體輸送法、單一源法、混合源法等。 [0048] 又,作為上述之堆積方法,舉例為使原料氣體或使原料氣體與反應性氣體僅藉由熱而反應並堆積薄膜之熱CVD,使用熱及電漿之電漿CVD,使用熱與光之光CVD,使用熱、光及電漿之光電漿CVD,將CVD之堆積反應分為基本過程,以分子等級進行階段性堆積之ALD。 [0049] 上述基體之材質舉例為例如矽;氮化矽、氮化鈦、氮化鉭、氧化鈦、氮化鈦、氧化釕、氧化鋯、氧化鉿、氧化鑭等之陶瓷;玻璃;金屬釕等之金屬。基體之形狀舉例為板狀、球狀、纖維狀、鱗片狀,基體表面可為平面,亦可成為溝槽構造等之三次元構造。 [0050] 且,作為上述製造條件,舉例為反應溫度(基體溫度)、反應壓力、堆積速度等。關於反應溫度,本發明之二氮雜二烯基化合物充分地反應之溫度的150℃以上為佳,150℃~400℃為更佳,200℃~350℃為特別佳。又,反應壓力於熱CVD或光CVD時,大氣壓~10Pa為佳,使用電漿時,2000Pa~10Pa為佳。 又,堆積速度可藉由原料之供給條件(氣化溫度、氣化壓力)、反應溫度、反應壓力而控制。堆積速度若太大則有所得薄膜特性惡化之情況,太小則有生產性產生問題之情況,因此0.01~100nm/分鐘為佳,1~50nm/分鐘為更佳。且,ALD法時,以循環次數進行控制以獲得所期望膜厚。 [0051] 作為上述製造條件進一步舉例為使薄膜形成用原料氣化成為蒸氣時之溫度或壓力。使薄膜形成用原料氣化成為蒸氣之步驟可在原料容器內進行,亦可在氣化室內進行。任一情況下,本發明之薄膜形成用原料在0~150℃蒸發為佳。又,於原料容器內或氣化室內使薄膜形成用原料氣化成為蒸氣時,原料容器內之壓力或氣化室內之壓力均佳為1~10000Pa。 [0052] 本發明之薄膜之製造方法除了採用ALD法,藉由上述輸送供給方法使薄膜形成用原料氣化成為蒸氣,將該蒸氣導入成膜腔室內之原料導入步驟以外,亦可具有藉由該蒸氣中之上述二氮雜二烯基化合物於上述基體表面形成前驅物薄膜之前驅物薄膜成膜步驟、將未反應之排氣之二氮雜二烯基化合物之排氣步驟,及使該前驅物薄膜與反應性氣體化學反應,於該基體表面形成含有上述金屬之薄膜之含金屬之薄膜形成步驟。 [0053] 以下,針對上述各步驟,詳細說明。藉由ALD法形成含有選自鎳原子及錳原子中至少1種之原子之金屬薄膜時,首先進行前述說明之原料導入步驟。使薄膜形成用原料成為蒸氣時之較佳溫度或壓力與上述說明者相同。接者,藉由導入堆積反應部之二氮雜二烯基化合物,於基體表面成膜前驅物薄膜(前驅物薄膜成膜步驟)。此時,亦可加熱基體、或加熱而堆積反應部施加熱。以該步驟成膜之前驅物薄膜為之二氮雜二烯基化合物一部分分解及/或反應而生成之薄膜,具有與目的之金屬薄膜不同之組成。進行本步驟時之基體溫度係室溫~500℃為佳,150~350℃為更佳。進行本步驟時之系(成膜腔室內)之壓力1~10000Pa為佳,10~1000Pa為更佳。 [0054] 接者,自堆積反應部排出未反應二氮雜二烯基化合物之氣體或副生之氣體(排氣步驟)。未反應之二氮雜二烯基化合物氣體或副生之氣體理想上係自堆積反應部完全排氣,但並無必要必定完全排氣。排氣方法有藉由氮氣、氦氣、氬氣等之惰性氣體吹拂系內之方法,藉由使系內減壓而排氣之方法,組合該等之方法等。減壓時之減壓度0.01~300Pa為佳,0.01~100Pa為更佳。 [0055] 接者,於堆積反應部導入反應性氣體,藉由該反應性氣體之作用或反應性氣體及熱之作用,自以先前之前驅物薄膜成膜步驟所得之前驅物薄膜形成目的之金屬薄膜(金屬薄膜形成步驟)。本步驟中,使熱作用時之溫度的室溫~500℃為佳,150~350℃為更佳。進行本步驟時之系(成膜腔室內)之壓力1~10000Pa為佳,10~1000 Pa為更佳。本發明之二氮雜二烯基化合物係與反應性氣體之反應性為良好,故可得到殘留含碳量為少的高品質的金屬薄膜。 [0056] 本發明的薄膜之製造方法,採用如上述之ALD法時,將由上述之原料導入步驟、前驅物薄膜成膜步驟、排氣步驟及金屬薄膜形成步驟所成之一連串操作之薄膜堆積設為1循環,可重複複數次該循環直至獲得必要膜厚之薄膜。該情況下,進行1循環後,與上述排氣步驟同樣地,自堆積反應部排出未反應之二氮雜二烯基化合物之化合物氣體及反應性氣體進一部排出副生之氣體後,進行下一循環為佳。 [0057] 再者,利用薄膜之ALD法之形成中,亦可施加電漿、光、電壓等之能量,亦可使用觸媒。施加該能量之時期及使用觸媒之時期並未特別限定,宜為例如於原料導入步驟中之二氮雜二烯基化合物氣體導入時,前驅物薄膜成膜步驟或薄膜形成步驟中之加溫時,排氣步驟之系內排氣時,薄膜形成步驟中之反應性氣體導入時,亦可為上述各步驟之間。 [0058] 又,本發明之薄膜之製造方法中,薄膜堆積後,為了獲得更良好之電特性,亦可在惰性環境下、氧化性環境下或還原性環境下進行退火處理,於必須埋入階差時,亦可設回焊步驟。該情況之溫度為200~1000℃,250~500℃為佳。 [0059] 使用本發明之薄膜形成用原料製造薄膜之裝置可使用周知的化學氣相成長法用裝置。作為具體的裝置之一例舉例為例如圖1所示之可藉冒泡供給前驅物而進行之裝置,或如圖2所示之具有氣化室之裝置。且,舉例為如圖3及圖4之可對反應性氣體進行電漿處理之裝置。不限於如圖1~圖4之單片式裝置,亦可使用利用批式爐可同時處理多數片之裝置。 [0060] 使用本發明之薄膜形成用原料所製造之薄膜係藉由適當選擇其他之前驅物、反應性氣體及製造條件,可成為金屬、氧化物陶瓷、氮化物陶瓷、玻璃等之所期望之種類之薄膜。已知該薄膜係示出各種之電特性及光學特性等,應用於各種之用途。例如,銅及含銅之薄膜係因高的導電性、高電遷移耐性、高熔點這樣的特性,應用作為LSI之配線材料。再者,鎳及含鎳之薄膜係主要可使用於電阻膜、阻隔膜等之電子零件之零件、磁性膜等之記錄媒體用之零件,或電極等之薄膜太陽能電池用零件等。 [實施例] [0061] 以下列舉實施例及評估例更詳細說明本發明。然而,本發明不受以下實施例之任何限制。 [0062] [製造例1] N,N’-二異丙基-丙烷-1,2-二醯亞胺之製造 於1L四口燒瓶中,加入異丙基胺197g(3.33mol)與脫水三氯甲烷496g(4.16mol),冷卻至10℃附近為止。將丙酮醛40%水溶液150g(0.833mol)以液溫成為10~14℃之方式花費1小時滴下於該溶液中。滴下結束後,於液溫10℃下攪拌2小時。之後,靜置反應液,分液有機層。更進一步,水層係以三氯甲烷(100g)進行2次萃取,回收有機層。集中全部之有機層,以硫酸鈉進行脫水、過濾後,以微減壓下油浴溫度60~70℃,進行脫溶劑。之後,以減壓下油浴溫度64℃,進行蒸餾。所得之餾分係淡黃色透明之液體,產量95.5g及產率74.0%。 [0063] (分析值) (1)質量分析m/z:154(M+) (2)元素分析C:72.2質量%、H:12.0質量%、N:17.9質量%(理論值;C:70.0質量%、H:11.8質量%、N:18.2質量%) [0064] [實施例1] 化合物No.1之製造 於1L四口燒瓶中,加入以上述所得到之N,N’-二異丙基-丙烷-1,2-二醯亞胺21.4g(138.9mmol)與脫水四氫呋喃(412g),以乾冰/IPA浴冷卻至-30℃為止。於其中,一點一點加入金屬鋰片0.988g(142.4mmol),使其於-10℃下反應。將該溶液,於氯化鎳9.0g(69.45mmol)與脫水四氫呋喃(412g)之懸濁液中,於-10℃前後下滴下後,昇溫至室溫使其反應15小時。之後,於油浴溫度65℃、微減壓下進行脫溶劑。放涼後,以脫水己烷再溶解,以膜過濾器過濾分離。所得到之濾液,於油浴溫度65℃、微減壓下進行脫溶劑,使其乾燥。將所得到之殘渣,以油浴溫度115℃、20Pa下進行蒸餾,得到紅黑色黏性液體之目的物。產量係5.8g,產率20.5%。藉由將所得到之目的物於大氣中放置,確認自燃性之有無時,自燃性為無。 [0065] (分析值) (1)1
NMR(溶劑:重苯)(化學位移:多重度:H數) (8.976:s:1)(3.151~3.087:m:1)(2.651~2.587:m:1)(1.937~1.870:m:12)(-1.408:s:3) (2)元素分析(金屬分析:ICP-AES、氯分析:TOX) Ni:15.9質量%、C:58.6質量%、H:10.0質量%、N:15.5質量%(理論值;Ni:16.0質量%、C:58.8質量%、H:9.88質量%、N:15.3質量%)、氯(TOX):未達10ppm [0066] [評估例1] 化合物之物性評估 對於化合物No.1及下述比較化合物1,藉由目視,觀察常壓30℃中之各化合物之狀態。再者,對於化合物No.1及下述比較化合物1,使用DSC,測定熱分解開始之溫度。再者,對於化合物No.1及下述比較化合物1,使用TG-DTA於減壓下,測定重量減少為50%時之溫度。結果表示如表1。 (減壓TG-DTA測定條件) 10Torr、Ar流量:50ml/分、昇溫速度:10℃/分、樣本量:約10mg [0067][0068][0069] 依據上述表1,化合物No.1及比較化合物1係於常壓30℃之條件下,為液體狀態之化合物,可了解任一者熱分解開始溫度為200℃以上。可了解化合物No.1比比較化合物1之熱分解開始溫度為15℃左右高。再者,由減壓TG-DTA之結果得知,雖然化合物No.1比比較化合物1之50質量%減少時之溫度略為高一些,可了解示出作為化學氣相成長用原料之充分的蒸氣壓。 [0070] [實施例2] 利用ALD法之金屬鎳薄膜之製造 將化合物No.1作為化學氣相成長用原料,使用圖1所示之化學氣相成長用裝置,藉由以下之條件的ALD法,於銅基板上製造金屬鎳薄膜。對於所得到之薄膜,利用X射線反射率法測定膜厚、利用X射線繞射法及X射線光電子光譜法(X-ray Photoelectron Spectroscopy)進行薄膜構造及薄膜組成之確認時,膜厚係7~8nm,膜組成係金屬鎳(利用XPS分析以Ni2p峰確認),薄膜中之殘留含碳量之檢測下限少於0.1atom%。每1循環所得之膜厚為0.05nm。 [0071] (條件) 反應溫度(基板溫度):250℃,反應性氣體:氫氣 (步驟) 將由下述(1)~(4)所成之一連串步驟設為1循環,重複150次循環: (1)於原料容器加熱溫度:100℃、原料容器內壓力:100Pa之條件下,將氣化之化學氣相成長用原料導入於成膜腔室內,於系壓力100Pa下,堆積30秒; (2)藉由5秒之氬吹拂,去除未反應原料及副生之氣體; (3)導入反應性氣體於成膜腔室,以系壓力100Pa反應30秒; (4)藉由5秒之氬吹拂,去除未反應原料及副生之氣體。 [0072] [比較例1] 除了使用上述比較化合物1作為化學氣相成長法原料以外,以與實施例2相同之方法製造金屬鎳薄膜。對於所得到之薄膜,利用X射線反射率法測定膜厚、利用X射線繞射法及X射線光電子光譜法進行薄膜構造及薄膜組成之確認時,膜厚係6nm,膜組成係金屬鎳(利用XPS分析以Ni2p峰確認),薄膜中之殘留含碳量係24atom%。每1循環所得之膜厚為0.04nm。 [0073] 依據以上之結果,了解在實施例2中,薄膜中之殘留含碳量少,可利用ALD法製造非常高品質的金屬鎳薄膜。另一方面,了解在比較例1中,確認所得到之金屬鎳薄膜中存在大量之殘留碳,不可製造品質佳的金屬鎳薄膜。 [0074] 尚,本國際申請係基於2016年8月29日申請之日本國專利申請第2016-166588號主張優先權,且將該日本專利申請之全內容納入本國際申請。
[0014] [圖1] 圖1係顯示本發明之薄膜之製造方法中可使用之化學氣相成長用裝置之一例之概要圖。 [圖2] 圖2係顯示本發明之薄膜之製造方法中可使用之化學氣相成長用裝置之另一例之概要圖。 [圖3] 圖3係顯示本發明之薄膜之製造方法中可使用之化學氣相成長用裝置之一例之概要圖。 [圖4] 圖4係顯示本發明之薄膜之製造方法中可使用之化學氣相成長用裝置之一例之概要圖。
Claims (4)
- 一種二氮雜二烯基化合物,其係以下述通式(I)表示:(式中,R1 係表示碳數1~6之直鏈或分支狀之烷基,M係表示鎳原子或錳原子)。
- 如請求項1之二氮雜二烯基化合物,其中上述通式(I)中,R1 為甲基。
- 一種薄膜形成用原料,其係含有如請求項1或2之二氮雜二烯基化合物而成。
- 一種薄膜之製造方法,其係將含有使如請求項3之薄膜形成用原料氣化而得之二氮雜二烯基化合物的蒸氣,導入設置有基體的成膜腔室內,使該二氮雜二烯基化合物分解及/或使其進行化學反應而於該基體之表面形成含有選自鎳原子及錳原子中至少1種之原子的薄膜。
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