TWI761333B - 薄膜形成用原料及薄膜的製造方法 - Google Patents
薄膜形成用原料及薄膜的製造方法 Download PDFInfo
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- TWI761333B TWI761333B TW106107233A TW106107233A TWI761333B TW I761333 B TWI761333 B TW I761333B TW 106107233 A TW106107233 A TW 106107233A TW 106107233 A TW106107233 A TW 106107233A TW I761333 B TWI761333 B TW I761333B
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- thin film
- raw material
- carbon atoms
- film formation
- zirconium
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- 239000002994 raw material Substances 0.000 title claims abstract description 94
- 239000010409 thin film Substances 0.000 title claims description 145
- 238000000034 method Methods 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052735 hafnium Chemical group 0.000 claims abstract description 15
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 32
- 230000008016 vaporization Effects 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 5
- 238000005755 formation reaction Methods 0.000 description 44
- -1 methylene, ethylene, propane-1,3-diyl Chemical group 0.000 description 42
- 239000002243 precursor Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 30
- 238000000231 atomic layer deposition Methods 0.000 description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 20
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- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 13
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
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- 239000010703 silicon Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 8
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 8
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- 239000012535 impurity Substances 0.000 description 7
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- 239000007791 liquid phase Substances 0.000 description 4
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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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
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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Abstract
一種薄膜形成用原料，其係含有以下述通式(1)表示之化合物而成：
式中，R1係表示碳原子數2~4之直鏈或分支狀之烷基，R2~R5係各自獨立表示碳原子數1~4之直鏈或分支狀之烷基，A係表示碳原子數1~4之烷二基，M係表示鈦、鋯或鉿；惟，M為鋯之時，A係碳原子數3或4之烷二基。M為鈦及鉿之時，A係碳原子數2或3之烷二基為佳。M為鋯之時，A係碳原子數3之烷二基為佳。
Description
本發明係關於一種含有特定之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的製造方法。
含有鈦、鋯或鉿之薄膜材料被應用於半導體、太陽能電池(photovoltaic cell)、TFT等之用途，其中主要使用作為半導體材料用之高介電材料。
作為上述薄膜的製造法，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、化學氣相成長法等，但包含ALD(Atomic Layer Deposition)法之化學氣相成長法(以下有時亦僅記載為CVD)法，由於具有組成控制性、階差被覆性優異，適於量產化，且可混成積體等之多種優點，故為最適之製造製程。
作為化學氣相成長法所使用之金屬供給源，
多數報告有各種原料。
例如於專利文獻1中，揭示作為可使用於ALD法或CVD法之材料而使用特定之鋯錯合物。又，於專利文獻2中，揭示作為可使用於ALD法或CVD法之材料而使用特定之金属錯合物。於專利文獻1及專利文獻2中，未具體的記載本發明之薄膜形成用原料。
[專利文獻1]韓國專利10-1263454號
[專利文獻2]韓國公開10-2014-0078534號
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，為得到高品質的薄膜而必須於高溫下進行成膜，故要求熱安定性高的薄膜形成用原料。又，可要求於方位比為10~200左右之溝中可均勻地形成薄膜之薄膜形成用原料。
本發明人等重複檢討之結果，發現含有特定之化合物之薄膜形成用原料可解決上述課題，因而完成本
發明。
本發明係提供一種薄膜形成用原料，其係含有以下述通式(1)表示之化合物而成：
(式中，R1係表示碳原子數2~4之直鏈或分支狀之烷基，R2~R5係各自獨立表示碳原子數1~4之直鏈或分支狀之烷基，A係表示碳原子數1~4之烷二基，M係表示鈦、鋯或鉿；惟，M為鋯之時，A係碳原子數3或4之烷二基)。
又，本發明係提供一種薄膜的製造方法，其係將含有使上述薄膜形成用原料氣化而得之以通式(1)表示之化合物的蒸氣，導入設置有基體的成膜腔室內，使該化合物分解及/或使其進行化學反應而於該基體之表面形成含有選自鈦、鋯及鉿中至少1種之原子的薄膜。
依據本發明，可獲得熱安定性高，於方位比為10~200左右之溝中可均勻地形成高品質的薄膜之薄膜形成用原料。本發明之薄膜形成用原料適合作為利用
CVD法之金屬薄膜形成用之原料。本發明之薄膜形成用原料可適用於ALD法，故特別適合作為達到上述效果之ALD法用薄膜形成用原料。
[圖1]圖1係顯示本發明之薄膜的製造方法中可使用之化學氣相成長用裝置之一例的概要圖。
[圖2]圖2係顯示本發明之薄膜的製造方法中可使用之化學氣相成長用裝置之另一例的概要圖。
[圖3]圖3係顯示本發明之薄膜的製造方法中可使用之化學氣相成長用裝置之一例的概要圖。
[圖4]圖4係顯示本發明之薄膜的製造方法中可使用之化學氣相成長用裝置之一例的概要圖。
本發明之薄膜形成用原料係含有以上述通式(1)表示之化合物，且可較佳地作為具有CVD法等之氣化步驟的薄膜製造方法之前驅物者，亦可使用ALD法形成薄膜。
上述通式(1)中，R1係表示碳原子數2~4之直鏈或分支狀之烷基，R2~R5係各自獨立表示碳原子數1~4之直鏈或分支狀之烷基，A係表示碳原子數1~4之烷
二基，M係表示鈦、鋯或鉿；惟，M為鋯之時，A係碳原子數3或4之烷二基。
作為以上述R1表示之碳原子數2~4之直鏈或分支狀之烷基係可舉例乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基等。又，作為上述R2~R5表示之碳原子數1~4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、第三丁基等。
作為以上述A表示之碳原子數1~4之烷二基係可舉例亞甲基、亞乙基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二基等。作為以上述A表示之碳原子數3或4之烷二基係可舉例丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二基等。
上述通式(1)中，M為鈦及鉿之時，A為碳原子數2或3之烷二基之時，熱安定性高，使用ALD法於成膜時，可對基體上之方位比為高的溝之部分均勻形成薄膜，故為佳，其中，為碳原子數3之烷二基之時，使用ALD法於成膜時，對基體上之方位比為高的溝之部分均勻地形成薄膜之效果為高，故為佳。M為鋯之時，A為碳原子數3之烷二基之時，使用ALD法於成膜時，對基體上之方位比為高的溝之部分均勻地形成薄膜之效果為高，故為佳。上述通式(1)中，R1為乙基、異丙基、第二丁基及第三丁基之任一者時，使用ALD法於成膜時，可對基體上之方位比為高的溝之部分均勻地形成薄膜，故為佳。
R2~R5之中1個以上為甲基之時，蒸氣壓為高，故為佳。其中，R2及R4為甲基且R3及R5為乙基之時，熔點低、輸送性為良好，故為佳。利用並未伴隨氣化步驟之MOD法之薄膜的製造方法時，R1~R5及A可對於所使用之溶劑的溶解性、薄膜形成反應等適當選擇。
作為以通式(1)表示之化合物之較佳具體例係可舉例下述化學式No.1~No.88表示之化合物。尚，下述化學式No.1~No.88中，「Me」表示甲基，「Et」表示乙基，「iPr」表示異丙基，「sBu」表示第二丁基，「tBu」表示第三丁基。
以本發明之薄膜形成用原料所含有之通式(1)所表示之化合物係依據其製造方法但並無特別地限制，可應用周知之反應而製造。例如，M為鈦之時，於甲苯等之溶劑中之四(二烷基胺)鈦中，使對應之構造的烷基胺烷基環戊二烯化合物於10~50℃之溫度條件下反應即可。M為鋯之時，於甲苯等之溶劑中，使對應之構造的烷基胺烷基環戊二烯化合物於四(二烷基胺)鋯中，於10~50℃之溫度條件下反應即可。M為鉿之時，於甲苯等
之溶劑中，使對應之構造的烷基胺烷基環戊二烯化合物於四(二烷基胺)鉿中，於10~50℃之溫度條件下反應即可。
本發明之薄膜形成用原料的形態可依據於適用該薄膜形成用原料之製造製程而相異。例如，製造僅包含選自鈦、鋯及鉿所成之群中金屬之薄膜時，本發明之薄膜形成用原料不含有以通式(1)表示之化合物以外之金屬化合物及半金屬化合物。另一方面，製造包含選自鈦、鋯及鉿所成之群中選出的金屬與選自鈦、鋯及鉿所成之群中選出的金屬以外之金屬及/半金屬之薄膜時，本發明之薄膜形成用原料，含有包含選自鈦、鋯及鉿所成之群中選出之金屬以外之金屬及/半金屬之之化合物(以下亦稱為「其他前驅物」)。本發明之薄膜形成用原料如後述，亦可進而含有有機溶劑及/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CVD法、ALD法，故特別作為化學氣相成長用原料(以下有時亦稱為「CVD用原料」)有用。
本發明之薄膜形成用原料為化學氣相成長用原料時，其形態可根據所使用的CVD法之輸送供給方法等方法而適當選擇。
作為上述之輸送供給方法，有將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/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/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(1)表示之化合物本身可使用作為CVD用原料。液體輸送法時，可將以上述通式(1)表示之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。又，該等CVD用原料亦可進而包含其他前驅物或親核性試藥。
又，於多成分系之CVD法中，有使CVD用原料各成分獨立氣化並供給之方法(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並供給之方法(以下有時亦記載為混合源法)。混合源法時，可將本發明之薄膜形成用原料係以通式(1)表示之化合物與其他前驅物之混合物或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而包含親核性試藥等。
上述有機溶劑並未特別限制，可使用周知之一般有機溶劑。作為有機溶劑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的烴類；吡啶、甲基吡啶等，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使用或混合兩種以上使用。使用該等有機溶劑時，將前驅物溶解於有機溶劑之溶液的CVD用原料中之前驅物全體量為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有以通式(1)表示之化合物以外之金屬化合物及半金屬化合物時，為以通式(1)表示之化合物的量，於本發明之薄膜形成用原料中除了以通式(1)表示之化合物以外又含有包含其他金屬之化合物及包含半金屬之化合物(其他前驅物)時，為以通式(1)表示之化合物及其他前驅物之合計量。
且，於多成分系之CVD法時，作為與本發明之薄膜形成用原料一起使用之其他前驅物並未特別限制，可使用CVD原料中所用之周知一般前驅物。
作為其他前驅物，可舉例具有下述作為配位基之化合物所成之群中選擇之1種或2種以上之矽或金屬之化合物：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、二烷胺基烷基、單烷胺基、二烷胺基、二胺、二(矽烷基-烷基)胺、二(烷基-矽烷基)胺、二矽烷基胺、烷氧基、烷氧基烷
基、聯胺、磷化物、腈、二烷胺基烷氧基、烷氧基烷基二烷基胺、矽氧基、二酮酸酯基、環戊二烯基、矽烷基、吡唑酸酯、胍酸酯、磷胍酸酯、脒酸酯、磷脒酸酯、酮醯亞胺酯、二酮亞胺酸酯(diketiminate)、羰基及磷脒酸酯。
作為其他前驅物之金屬種，舉例為鎂、鈣、鍶、鋇、鐳、鈧、釔、釩、鈮、鉭、鉻、鉬、鎢、錳、鐵、鋨、鈷、銠、銥、鎳、鈀、鉑、銅、銀、金、鋅、鎘、鋁、鎵、銦、鍺、錫、鉛、銻、鉍、鑭、鈰、鐠、釹釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿。
上述之其他前驅物為本技藝領域中習知者，其製造方法亦為習知。若舉製造方法之一例，於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。此處，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。
上述之其他前驅物，於單一源法時，較佳為熱及/氧化分解行為與以通式(1)表示之化合物類似之化合物，於混合源法時，除了熱及/氧化分解行為類似以外，較佳為混合時不引起化學反應等之變質者。
作為上述之其他前驅物係可舉例如包含稀土類元素之前驅物。作為包含稀土類元素之前驅物係可舉例以下述式(III-1)~(III-3)表示之化合物。
(式中，M2表示稀土類原子，Ra及Rb各獨立地表示可經鹵原子取代之鏈中可包含氧原子之碳原子數1~20之烷基，Rc表示碳原子數1~8之烷基，Re及Rf各獨立地表示氫原子或碳原子數1~3之烷基，Rg及Rj各獨立地表示氫原子或碳原子數1~4之烷基，p’表示0~3之整數，r’表示0~2之整數)。
包含上述之稀土類元素之其他前驅物中，M2表示之稀土類原子舉例為鈧、釔、鑭、鈰、鐠、釹、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿、鎦。作為以Ra及Rb表示之，可經鹵原子取代之鏈中可包含氧原子之碳原子數1~20之烷基可舉例甲基、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、正辛基、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。又，作為以Rc表示之碳原子數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、正辛基、異辛基、第三辛基、2-乙基己基等。又，作為以Re及Rf表示之碳原子數1~3之烷基係可舉例甲基、乙基、丙基、2-丙基等，作為以Rg及Rj表示之碳原子數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。
又，於本發明之薄膜形成用材料中，根據需要，為了賦予以上述通式(1)表示之化合物及其他前驅物之安定性，亦可含有親核性試藥。作為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、二三甲基乙醯基甲烷(dipivaloylmethane)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，較佳為0.1莫耳~10莫耳之範圍，更佳為1~4莫耳。
本發明之薄膜形成用原料極力不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原素100ppb以下為佳，較佳為10ppb以下，總量計係1ppm以下為佳，較佳為100ppb以下。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。且，雜質鹵素分100ppm以下為佳，較佳為10ppm以下，最佳為1ppm以下。雜質有機分總量計係500ppm以下為佳，較佳為50ppm以下，最佳為10ppm以下。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，故金屬化合物、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。金屬化合物、有機溶劑及親核性試藥各水分量10ppm以下為佳，較佳為1ppm以下。
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，較佳極力不含顆粒。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中較佳為1000個以下，大於0.2μm之粒子數於液相1ml中最佳為100個以下。
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的製造方法，為將本發明之薄膜形成用原料氣化之蒸氣以及根據需要使用之反應性氣體導入設置基體之成膜腔室內，其次，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。
作為上述根據需要使用之反應性氣體，例如作為氧化性者係舉例氧、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，作為還原性者係舉例氫，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1種或2種以上。
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。
又，作為上述之堆積方法係舉例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。
作為上述基體之材質係舉例矽；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。作為基體之形狀係舉例板狀、球狀、纖維狀、鱗片狀，基體表面可為平面，亦可成為具有方位比為10~200左右之溝槽(溝)溝槽構造等之三次元構造。
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，以通式(1)表示之化合物充分反應之溫度的100℃以上為佳，較佳為150℃~400℃。以通式(1)表示之之化合物由於在未達300℃時可熱分解，故特佳為150℃~250℃。又，反應壓力於熱CVD或光CVD時，大氣壓~10Pa為佳，使用電漿時，為佳2000Pa~10Pa。
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，太小時有生產性產生問題之時，因此0.01~100nm/分鐘為佳，較佳為1~50nm/分鐘。且，ALD法時，以循環次數進行控制以獲得所期望膜厚。
作為上述製造條件進而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佳於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，原料容器內或氣化室內之壓力均為1~10000Pa為佳。
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以上述通式(1)表示之化合物於基體表面形成前驅物薄膜之前驅物薄膜成膜步驟，將未反應之薄膜形成用原料排氣之排氣步驟，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金屬之薄膜之含有金屬之薄膜形成步驟。
以下，針對上述各步驟，以形成金屬氧化物薄膜之時為例詳細說明。藉由ALD法形成金屬氧化物薄膜時，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。其次，藉由導入堆積反應部之以通式(1)表示之化合物，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、或加熱堆積反應部而施加熱。以該步驟成膜之前驅物薄膜為金屬氧化物薄膜、或以通式(1)表示之化合物之一部分分解及/或反應而生成之薄膜，具有與目的之金屬氧化物薄膜不同之組成。進行本步驟時之基體溫度之室溫~500℃為佳，較佳為150~350℃。進行本步驟時之系(成膜腔室內)之壓力1~10000Pa為佳，較佳為10~1000Pa。
其次，自堆積反應部排出未反應之薄膜形成用原料氣體或副生之氣體(排氣步驟)。未反應之薄膜形成用原料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。減壓時之減壓度係0.01~300Pa為佳，較佳為0.01~100Pa。
其次，於堆積反應部導入氧化性氣體，藉由該氧化性氣體之作用或氧化性氣體及熱之作用，自以之前之前驅物薄膜成膜步驟所得之前驅物薄膜形成金屬氧化物薄膜(含有金屬氧化物之薄膜形成步驟)。本步驟中，作用熱時之溫度係室溫~500℃為佳，較佳為150~350℃。進行本步驟時之系(成膜腔室內)之壓力佳為1~10000Pa，較佳為10~1000Pa。本發明之薄膜形成用原料與氧化性氣體之反應性良好，可獲得金屬氧化物薄膜。
本發明之薄膜之製造方法中，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、排氣步驟及含有金屬氧化物之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，較佳與上述排氣步驟同樣地，自堆積反應部排出未反應之薄膜形成用原料及反應性氣體(形成金屬氧化物薄膜時為氧化性氣體)進而排出副生之氣體後，進行下一循環。
又，金屬氧化物薄膜之藉由ALD法的形成
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本發明之薄膜用形成用原料氣體導入時、前驅物薄膜成膜步驟或含有金屬氧化物之薄膜形成步驟中之加溫時、排氣步驟之系內排氣時、含有金屬氧化物之薄膜形成步驟中之氧化性氣體導入時，亦可為上述各步驟之間。
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，亦可於惰性環境下、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℃，較佳為250~500℃。
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之化學氣相成長法用裝置。具體之裝置舉例為例如圖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。
使用本發明之薄膜形成用原料製造之薄膜，藉由適當選擇其他前驅物、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、玻璃等之期望種類之薄膜。已知該薄膜顯示各種電特性及光學特性等，已應用於各種用途。例如，應用於半導體、太陽能電池、TFT等
之用途，其中，主要可使用作為半導體材料用之高介電材料。
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。
將化合物No.34作為化學氣相成長用原料，使用圖1所示之ALD裝置藉由以下條件之ALD法，於形成直徑220nm、深8600nm(方位比39.1)之溝之矽基板上製造氧化鋯薄膜。針對所得薄膜，利用X射線反射率法測定膜厚、利用FE-SEM之觀察截面、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後，溝所無法形成之部分中薄膜之膜厚為3~6nm，且溝部分亦以均勻的厚度形成薄膜。薄膜之組成為氧化鋯(利用XPS分析由Zr3d及O1s之峰確認)，且，碳含量少於檢測下限之0.1atom%。每1循環所得之膜厚為0.02~0.04nm。
反應溫度(基板溫度)：210℃，反應性氣體：臭氧
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)導入於原料容器壓熱溫度140℃、原料容器內壓力10Pa之條件氣化之化學氣相成長用原料之蒸氣，以系壓20Pa堆積20秒；(2)藉由30秒之氬吹拂，去除未反應原料；(3)導入反應性氣體，以系壓力20Pa反應20秒；(4)藉由30秒之氬吹拂，去除未反應原料。
除了將下述之比較化合物1作為化學氣相成長用原料以外，與以實施例1同樣之條件，嘗試於矽基板上製造氧化鋯薄膜。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。溝所無法形成之部分中薄膜之膜厚為3~4nm，但溝部分以不均勻的厚度形成薄膜。(於溝之底部中，薄膜於大致不形成的狀態，除了於溝之底部以外，形成膜厚3~6nm之薄膜)。薄膜之組成係氧化鋯(利用XPS分析，以Zr3d及O1s之峰確認)，且薄膜中之碳含有量係8atom%。每1循環所得之膜厚為0.02~0.04nm。
除了將下述之比較化合物2作為化學氣相成長用原料以外，與以實施例1同樣之條件，嘗試於矽基板上製造氧化鋯薄膜。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。溝所無法形成之部分中薄膜之膜厚為3~4nm，但溝部分以不均勻的厚度形成薄膜。(於溝之底部中，薄膜大致不形成的狀態，除了於溝之底部以外，膜厚3~6nm之薄膜被形成)。薄膜之組成係氧化鋯(利用XPS分析，以Zr3d及O1s之峰確認)，且薄膜中之碳含有量係8atom%。每1循環所得之膜厚為0.02~0.04nm。
在實施例1中，可得到高品質的氧化鋯薄膜。又，化合物No.34之熱安定性為高，可了解矽基板上之方位比為高的溝之部分亦可形成均勻地高品質的薄膜。另一方面，於比較例1及比較例2中，於矽基板上之方位比為高的溝之部分，無法以均勻的厚度形成薄膜，且殘留於薄膜中之碳成分為多，故可了解無法得到高品質的氧化鋯薄膜。
將化合物No.58作為化學氣相成長用原料，使用圖1所示之ALD裝置藉由以下條件之ALD法，於形成直徑220nm、深8600nm之溝之矽基板上製造氧化鉿薄膜。對所得薄膜，利用X射線反射率法測定膜厚、利用FE-SEM觀察截面、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後，溝所無法形成之部分中薄膜之膜厚為3~6nm，且溝部分亦以均勻的厚度形成薄膜。薄膜之組成為氧化鉿(利用XPS分析以Hf4f及O1s之峰確認)，且，薄膜中之碳含量少於檢測下限之
0.1atom%。每1循環所得之膜厚為0.02~0.04nm。
反應溫度(基板溫度)：280℃，反應性氣體：臭氧
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)導入於原料容器加熱溫度140℃、原料容器內壓力10Pa之條件氣化之化學氣相成長用原料之蒸氣，以系壓20Pa堆積20秒；
(2)藉由30秒之氬吹拂，去除未反應原料；(3)導入反應性氣體，以系壓力20Pa反應20秒；(4)藉由30秒之氬吹拂，去除未反應原料。
除了將化合物No.66作為化學氣相成長用原料以外，與以實施例2同樣之條件，於矽基板上製造氧化鉿薄膜。對於所得到之薄膜，利用X射線反射率法測定膜厚、利用FE-SEM觀察截面、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。溝所無法形成之部分中薄膜之膜厚為3~6nm，且溝部分以均勻的厚度形成薄膜。薄膜之組成係氧化鉿(利用XPS分析，以Hf4f及O1s之峰確認)，且薄膜中之碳含量少於檢測下限之
0.1atom%。每1循環所得之膜厚為0.02~0.04nm。
在實施例2及3中，可得到皆為高品質的氧化鉿薄膜。又，化合物No.58及66之熱安定性為高，故可了解矽基板上之方位比為高的溝之部分亦可形成均勻地高品質的薄膜。
尚，本國際申請係基於2016年5月23日申請之日本國專利申請第2016-102628號，主張優先權，且將該日本國際申請之全內容納入本國際申請。
Claims (3)
- 一種薄膜形成用原料，其係含有以下述通式(1)表示之化合物而成：
- 如請求項1之薄膜形成用原料，其係ALD法用薄膜形成用原料。
- 一種薄膜的製造方法，其係將含有使如請求項1或2之薄膜形成用原料氣化而得之以通式(1)表示之化合物的蒸氣，導入設置有基體的成膜腔室內，使該化合物分解及/或使其進行化學反應而於該基體之表面形成含有選自鈦、鋯及鉿中至少1種之原子的薄膜。
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