CN109154080A - 薄膜形成用原料及薄膜的制造方法 - Google Patents
薄膜形成用原料及薄膜的制造方法 Download PDFInfo
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- CN109154080A CN109154080A CN201780031611.4A CN201780031611A CN109154080A CN 109154080 A CN109154080 A CN 109154080A CN 201780031611 A CN201780031611 A CN 201780031611A CN 109154080 A CN109154080 A CN 109154080A
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- 238000000137 annealing Methods 0.000 description 1
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- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical class N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 238000006884 silylation reaction Methods 0.000 description 1
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- 239000011734 sodium Substances 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
- 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- C23C16/04—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
-
- 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
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Abstract
一种薄膜形成用原料,其含有以下述通式(1)表示的化合物而成:【化1】式中,R1是表示碳原子数2~4的直链或分支状的烷基,R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示碳原子数1~4的烷二基,M是表示钛、锆或铪;但,M为锆时,A是碳原子数3或4的烷二基。M为钛及铪时,A是碳原子数2或3的烷二基是优选的。M为锆时,A是碳原子数3的烷二基是优选的。
Description
【技术领域】
本发明涉及一种含有特定的化合物而成的薄膜形成用原料及使用该薄膜形成用原料的薄膜的制造方法。
【背景技术】
含有钛、锆或铪的薄膜材料被应用于半导体、太阳能电池(photovoltaic cell)、TFT等的用途,其中主要使用作为半导体材料用的高介电材料。
作为上述薄膜的制造法,可举例为溅镀法、离子镀敷法、涂布热分解法或溶凝胶法等的MOD法、化学气相成长法等,但包含ALD(Atomic Layer Deposition)法的化学气相成长法(以下有时也简单地记载为CVD)法,由于具有组成控制性、逐步包覆性优异,适于量产化,且可以混合累积(hybrid accumulation)等的多种优点,故为最适的制造过程。
作为化学气相成长法所使用的金属供给源,多数报告有各种原料。
例如在专利文献1中,公开了作为可使用于CVD法或ALD法的材料而使用特定的锆配合物。另外,在专利文献2中,公开了作为可使用于CVD法或ALD法的材料而使用特定的金属配合物。在专利文献1及专利文献2中,未具体记载本发明的薄膜形成用原料。
[现有技术文献]
[专利文献]
[专利文献1]韩国专利10-1263454号
[专利文献2]韩国公开10-2014-0078534号
【发明内容】
[发明要解决的课题]
使化学气相成长用原料等气化而在基材表面形成含有金属的薄膜时,为得到高品质的薄膜而必须在高温下进行成膜,故要求热稳定性高的薄膜形成用原料。另外,可要求于宽高比(aspect ratio)为10~200左右的沟中可均匀地形成薄膜的薄膜形成用原料。
[用以解决课题的手段]
本发明人等重复讨论的结果,发现含有特定的化合物的薄膜形成用原料可解决上述课题,因而完成本发明。
本发明提供一种薄膜形成用原料,其含有以下述通式(1)表示的化合物而成:
[化1]
(式中,R1是表示碳原子数2~4的直链或分支状的烷基,R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示碳原子数1~4的烷二基,M是表示钛、锆或铪。但,M为锆时,A是碳原子数3或4的烷二基)。
另外,本发明提供一种薄膜的制造方法,其将含有使上述薄膜形成用原料气化而得到的通式(1)表示的化合物的蒸气,导入设置有基体的成膜腔室内,使该化合物分解及/或使其进行化学反应而在该基体的表面形成含有选自钛、锆及铪中至少1种的原子的薄膜。
[发明的效果]
依据本发明,可获得热稳定性高,于宽高比为10~200左右的沟中可均匀地形成高品质的薄膜的薄膜形成用原料。本发明的薄膜形成用原料适合作为利用CVD法的金属薄膜形成用的原料。本发明的薄膜形成用原料可适用于ALD法,故特别适合作为达到上述效果的ALD法用薄膜形成用原料。
【附图的简单说明】
[图1]图1为表示本发明的薄膜的制造方法中可使用的化学气相成长用装置的一例的概要图。
[图2]图2为表示本发明的薄膜的制造方法中可使用的化学气相成长用装置的另一例的概要图。
[图3]图3为表示本发明的薄膜的制造方法中可使用的化学气相成长用装置的一例的概要图。
[图4]图4为表示本发明的薄膜的制造方法中可使用的化学气相成长用装置的一例的概要图。
【具体实施方式】
本发明的薄膜形成用原料含有以上述通式(1)表示的化合物,且合适地作为具有CVD法等的气化步骤的薄膜制造方法的前体,也可使用ALD法形成薄膜。
上述通式(1)中,R1是表示碳原子数2~4的直链或分支状的烷基,R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示碳原子数1~4的烷二基,M是表示钛、锆或铪;但,M为锆时,A是碳原子数3或4的烷二基。
作为以上述R1表示的碳原子数2~4的直链或分支状的烷基可举例乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基等。另外,作为上述R2~R5表示的碳原子数1~4的直链或分支状的烷基可举例甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基等。
作为以上述A表示的碳原子数1~4的烷二基可举例亚甲基、亚乙基、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。作为以上述A表示的碳原子数3或4的烷二基可举例丙烷-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为钛及铪时,A为碳原子数2或3的烷二基时,热稳定性高,使用ALD法成膜时,可对基体上的宽高比高的沟的部分均匀形成薄膜,故是优选的,其中,为碳原子数3的烷二基时,使用ALD法成膜时,对基体上的宽高比高的沟的部分均匀地形成薄膜的效果高,故是优选的。M为锆时,A为碳原子数3的烷二基时,使用ALD法成膜时,对基体上的宽高比高的沟的部分均匀地形成薄膜的效果高,故是优选的。上述通式(1)中,R1为乙基、异丙基、仲丁基及叔丁基的任一者时,使用ALD法成膜时,可对基体上的宽高比高的沟的部分均匀地形成薄膜,故是优选的。R2~R5芝中1个以上为甲基时,蒸气压高,故是优选的。其中,R2及R4为甲基且R3及R5为乙基时,熔点低、输送性良好,故是优选的。利用并未伴随气化步骤的MOD法的薄膜的制造方法时,R1~R5及A可对于所使用的溶剂的溶解性、薄膜形成反应等适当选择。
作为以通式(1)表示的化合物的优选具体例可举例下述化学式No.1~No.88表示的化合物。需要说明的是,下述化学式No.1~No.88中,“Me”表示甲基,“Et”表示乙基,“iPr”表示异丙基,“sBu”表示仲丁基,“tBu”表示叔丁基。
[化3]
[化4]
[化5]
[化6]
[化7]
以本发明的薄膜形成用原料所含有的通式(1)所表示的化合物依据其制造方法但并无特别地限制,可应用周知的反应而制造。例如,M为钛时,在甲苯等的溶剂中的四(二烷基氨基)钛中,使对应的构造的烷基胺烷基环戊二烯化合物在10~50℃的温度条件下反应即可。M为锆时,在甲苯等的溶剂中,使对应的构造的烷基胺烷基环戊二烯化合物于四(二烷基氨基)锆中,在10~50℃的温度条件下反应即可。M为铪时,在甲苯等的溶剂中,使对应的构造的烷基胺烷基环戊二烯化合物于四(二烷基氨基)铪中,在10~50℃的温度条件下反应即可。
本发明的薄膜形成用原料的形态可依据适用该薄膜形成用原料的制造过程而相异。例如,制造仅包含选自钛、锆及铪所成的群中金属的薄膜时,本发明的薄膜形成用原料不含有以通式(1)表示的化合物以外的金属化合物及半金属化合物。另一方面,制造包含选自钛、锆及铪所成的群中选出的金属与选自钛、锆及铪所成的群中选出的金属以外的金属及/半金属的薄膜时,本发明的薄膜形成用原料,含有包含选自钛、锆及铪所成的群中选出的金属以外的金属及/半金属的的化合物(以下也称为“其他前体”)。本发明的薄膜形成用原料如后述,也可进而含有有机溶剂及/亲核性试药。本发明的薄膜形成用原料如上述说明,由于适用于CVD法、ALD法,故特别作为化学气相成长用原料(以下有时也称为“CVD用原料”)有用。
本发明的薄膜形成用原料为化学气相成长用原料时,其形态可根据所使用的CVD法的输送供给方法等方法而适当选择。
作为上述的输送供给方法,有将CVD用原料于储存该原料的容器(以下有时也简单记载为原料容器)中加热及/减压而气化为蒸气,将该蒸气与根据需要使用的氩、氮、氦等的载气一起导入设置基体的成膜腔室内(以下有时也记载为堆积反应部)的气体输送法,将CVD用原料以液体或溶液状态输送至气化室,在气化室通过加热及/减压而气化为蒸气,将该蒸气导入成膜腔室内的液体输送法。气体输送法时,以上述通式(1)表示的化合物本身可使用作为CVD用原料。液体输送法时,可将以上述通式(1)表示的化合物本身或该化合物溶于有机溶剂中的溶液作为CVD用原料。另外,这些CVD用原料也可进而包含其他前体或亲核性试药等。
另外,在多成分体系的CVD法中,有使CVD用原料各成分独立气化并供给的方法(以下有时也记载为单一源法)与使多成分原料预先以期望组成混合的混合原料气化并供给的方法(以下有时也记载为混合源法)。混合源法时,可将本发明的薄膜形成用原料可以将通式(1)表示的化合物与其他前体的混合物或将该混合物溶于有机溶剂的混合溶液作为CVD用原料。该混合物或混合溶液也可进而包含亲核性试药等。
上述有机溶剂并未特别限制,可使用周知的一般有机溶剂。作为有机溶剂举例为例如乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等的乙酸酯类;四氢呋喃、四氢吡喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二丁醚、二烷等醚类;甲基丁基酮、甲基异丁基酮、乙基丁基酮、二丙基酮、二异丁基酮、甲基戊基酮、环己酮、甲基环己酮等的酮类;己烷、环己烷、甲基环己烷、二甲基环己烷、乙基环己烷、庚烷、辛烷、甲苯、二甲苯等的烃类;1-氰基丙烷、1-氰基丁烷、1-氰基己垸、氰基环己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基环己烷、1,4-二氰基苯等的具有氰基的烃类;吡啶、甲基吡啶等,这些有机溶剂可根据溶质的溶解性、使用温度与沸点、起火点的关系等而单独使用或混合两种以上使用。使用这些有机溶剂时,将前体溶解于有机溶剂的溶液的CVD用原料中的前体全体量为0.01~2.0摩尔/升是优选的,特优选为0.05~1.0摩尔/升。所谓前体全体量,于本发明的薄膜形成用原料不含有以通式(1)表示的化合物以外的金属化合物及半金属化合物时,为以通式(1)表示的化合物的量,于本发明的薄膜形成用原料中除了以通式(1)表示的化合物以外又含有包含其他金属的化合物及包含半金属的化合物(其他前体)时,为以通式(1)表示的化合物及其他前体的合计量。
而且,在多成分体系的CVD法时,作为与本发明的薄膜形成用原料一起使用的其他前体并未特别限制,可使用CVD原料中所用的周知一般前体。
作为其他前体,可举例具有下述作为配位基的化合物所成的群中选择的1种或2种以上的硅或金属的化合物:氢化物、氢氧化物、卤化物、叠氮化物、烷基、烯基、环烷基、芳基、炔基、氨基、二烷氨基烷基、单烷氨基、二烷氨基、二胺、二(硅烷基-烷基)氨基、二(烷基-硅烷基)氨基、二硅烷基氨基、烷氧基、烷氧基烷基、联胺、磷化物、腈、二烷氨基烷氧基、烷氧基烷基二烷基胺、硅氧基、二酮酸酯基、环戊二烯基、硅烷基、吡唑酸酯(pyrazolate)、胍酸酯(guanidinate)、磷胍酸酯、脒酸酯、磷米酸酯、酮亚胺酸酯(ketoiminate)、二酮亚胺酸酯(diketoiminate)、羰基及磷脒酸酯(phosphoamidinate)。
作为其他前体的金属种,举例为镁、钙、锶、钡、镭、钪、钇、钒、铌、钽、铬、钼、钨、锰、铁、锇、钴、铑、铱、镍、钯、铂、铜、银、金、锌、镉、铝、镓、铟、锗、锡、铅、锑、铋、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱。
上述的其他前体为本技术领域中公知的,其制造方法也为公知。若举制造方法的一例,在例如使用醇化合物作为有机配位基时,通过使如前述的金属无机盐或其水合物与该醇化合物的碱金属烷氧化物反应,可制造前体。此处,金属的无机盐或其水合物可举例为金属的卤化物、硝酸盐等,作为碱金属烷氧化物可举例为烷氧基钠、烷氧基锂、烷氧基钾等。
上述的其他前体,在单一源法时,优选为热及/氧化分解行为与以通式(1)表示的化合物类似的化合物,在混合源法时,除了热及/氧化分解行为类似以外,优选为混合时不引起因化学反应等产生的变质的物质。
作为上述的其他前体可举例如包含稀土类元素的前体。作为包含稀土类元素的前体可举例以下述式(III-1)~(III-3)表示的化合物。
[化8]
(式中,M2表示稀土类原子,Ra及Rb各独立地表示可经卤原子取代的、链中可包含氧原子的碳原子数1~20的烷基,Rc表示碳原子数1~8的烷基,Re及Rf各独立地表示氢原子或碳原子数1~3的烷基,Rg及Rj各独立地表示氢原子或碳原子数1~4的烷基,p’表示0~3的整数,r’表示0~2的整数)。
包含上述的稀土类元素的其他前体中,M2表示的稀土类原子举例为钪、钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥等。作为以Ra及Rb表示的、可经卤原子取代的、链中可包含氧原子的碳原子数1~20的烷基可举例甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基、戊基、异戊基、新戊基、叔戊基、己基、环己基、1-甲基环己基、庚基、3-庚基、异庚基、叔庚基、正辛基、异辛基、叔辛基、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-异丙氧基-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。另外,作为以Rc表示的碳原子数1~8的烷基可举例甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基、戊基、异戊基、新戊基、叔戊基、己基、1-乙基戊基、环己基、1-甲基环己基、庚基、异庚基、叔庚基、正辛基、异辛基、叔辛基、2-乙基己基等。另外,作为以Re及Rf表示的碳原子数1~3的烷基可举例甲基、乙基、丙基、2-丙基等,作为以Rg及Rj表示的碳原子数1~4的烷基可举例甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基等。
另外,于本发明的薄膜形成用材料中,根据需要,为了赋予以上述通式(1)表示的化合物及其他前体的稳定性,也可含有亲核性试药。作为亲核性试药举例为甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚等的乙二醇醚类,18-冠状醚-6、二环己基-18-冠状醚-6、24-冠状醚-8、二环己基-24-冠状醚-8、二苯并-24-冠状醚-8等的冠状醚类,乙二胺、N,N’-四甲基乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、1,1,4,7,7-五甲基二亚乙基三胺、1,1,4,7,10,10-六甲基三亚乙基四胺、三乙氧基三亚乙基胺等的聚胺类,四氮杂环十四烷(cyclam)、四氮杂环十二烷(cyclen)等的环状聚胺类、吡啶、吡咯烷、哌啶、吗啉、N-甲基吡咯烷、N-甲基哌啶、N-甲基吗啉、四氢呋喃、四氢吡喃、1,4-二烷、唑、噻唑、氧硫杂环戊烷(oxathiolane)等的杂环化合物类、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸-2-甲氧基乙酯等的β-酮酯类或乙酰丙酮、2,4-己二酮、2,4-庚二酮、3,5-庚二酮、二特戊酰基甲烷(dipivaloyl methane)等的β-二酮类,这些亲核性试药的使用量,对于前体全体的量1摩尔,更优选为0.1摩尔~10摩尔的范围,更优选为1~4摩尔。
本发明的薄膜形成用原料极力地不含构成其的成分以外的杂质金属元素分、杂质氯等的杂质卤素分及杂质有机分。杂质金属元素分的每种元素100ppb以下是优选的,更优选为10ppb以下,总量计为1ppm以下是优选的,更优选为100ppb以下。尤其,使用作为LSI的闸极绝缘膜、闸极膜、障壁层时,必须减少对所得薄膜的电特性有影响的碱金属元素及碱土类金属元素的含量。而且,杂质卤素分100ppm以下是优选的,更优选为10ppm以下,最优选为1ppm以下。杂质有机分总量计为500ppm以下是优选的,更优选为50ppm以下,最优选为10ppm以下。另外,由于水分是化学气相成长用原料中的颗粒发生或薄膜形成中的颗粒发生的原因,故金属化合物、有机溶剂及亲核性试药中,为了减低各自的水分,使用时可以预先尽可能去除水分。金属化合物、有机溶剂及亲核性试药各自的水分量10ppm以下是优选的,更优选为1ppm以下。
另外,本发明的薄膜形成用原料,为了减低或防止所形成的薄膜的颗粒污染,优选极力不含颗粒。具体而言,在液相的通过光散射式液中粒子检测器的颗粒测定中,大于0.3μm的粒子数在液相1ml中100个以下是优选的,大于0.2μm的粒子数在液相1ml中更优选为1000个以下,大于0.2μm的粒子数在液相1ml中最优选为100个以下。
作为使用本发明的薄膜形成用原料制造薄膜的本发明的薄膜的制造方法,为将本发明的薄膜形成用原料气化的蒸气以及根据需要使用的反应性气体导入设置基体的成膜腔室内,其次,使前体于基体上分解及/或化学反应,于基体表面成长并堆积含金属的薄膜的CVD法。原料的输送供给方法、堆积方法、制造条件、制造装置等并未特别受到限制,可使用周知的一般条件及方法。
作为上述根据需要使用的反应性气体,例如作为氧化性的物质可举例氧、臭氧、二氧化氮、一氧化氮、水蒸气、过氧化氢、甲酸、乙酸、乙酸酐等,作为还原性的物质可举例氢,且作为制造氮化物的物质,举例为单烷基胺、二烷基胺、三烷基胺、亚烷基二胺等的有机胺化合物、联胺、氨等,这些可使用1种或2种以上。
而且,作为上述输送供给方法,举例为前述的气体输送法、液体输送法、单一源法、混合源法等。
另外,作为上述的堆积方法,可举例使原料气体或使原料气体与反应性气体仅通过热而反应并堆积薄膜的热CVD,使用热及等离子体(plasma)的等离子体CVD,使用热与光的光CVD,使用热、光及等离子体的光等离子体CVD,将CVD的堆积反应分为基本过程,以分子等级进行阶段性堆积的ALD。
作为上述基体的材质可举例硅;氮化硅、氮化钛、氮化钽、氧化钛、氮化钛、氧化钌、氧化锆、氧化铪、氧化镧等的陶瓷;玻璃;金属钌等的金属。作为基体的形状可举例板状、球状、纤维状、鳞片状,基体表面可为平面,也可成为具有宽高比为10~200左右的沟槽(沟)沟槽构造等的三维构造。
而且,作为上述制造条件,举例为反应温度(基体温度)、反应压力、堆积速度等。关于反应温度,以通式(1)表示的化合物充分反应的温度的100℃以上是优选的,更优选为150℃~400℃。以通式(1)表示的的化合物由于在未达300℃时可热分解,故特优选为150℃~250℃。另外,反应压力于热CVD或光CVD时,大气压~10Pa是优选的,使用等离子体时,优选2000Pa~10Pa。
另外,堆积速度可通过原料的供给条件(气化温度、气化压力)、反应温度、反应压力而控制。堆积速度若大,则有所得薄膜特性恶化的情况,若小时,有产生生产性问题时,因此0.01~100nm/分钟是优选的,更优选为1~50nm/分钟。而且,ALD法时,以循环次数进行控制以获得所期望膜厚。
作为上述制造条件进而举例为使薄膜形成用原料气化成为蒸气时的温度或压力。使薄膜形成用原料气化成为蒸气的步骤可在原料容器内进行,也可在气化室内进行。任一情况下,本发明的薄膜形成用原料在0~150℃蒸发是优选的。另外,于原料容器内或气化室内使薄膜形成用原料气化成为蒸气时,原料容器内或气化室内的压力均为1~10000Pa是优选的。
本发明的薄膜的制造方法除了采用ALD法,通过上述输送供给方法使薄膜形成用原料气化成蒸气,将该蒸气导入成膜腔室内的原料导入步骤以外,也可具有通过该蒸气中的以上述通式(1)表示的化合物于基体表面形成前体薄膜的前体薄膜成膜步骤,将未反应的薄膜形成用原料排气的排气步骤,及使该前体薄膜与反应性气体化学反应,在该基体表面形成含有金属的薄膜的含有金属的薄膜形成步骤。
以下,针对上述各步骤,以形成金属氧化物薄膜时为例详细说明。通过ALD法形成金属氧化物薄膜时,首先进行前述说明的原料导入步骤。使薄膜形成用原料成为蒸气时的优选温度或压力与上述说明的相同。其次,通过导入堆积反应部的以通式(1)表示的化合物,于基体表面成膜前体薄膜(前体薄膜成膜步骤)。此时,也可加热基体、或加热堆积反应部而施加热。以该步骤成膜的前体薄膜为金属氧化物薄膜、或以通式(1)表示的化合物的一部分分解及/或反应而生成的薄膜,具有与目的的金属氧化物薄膜不同的组成。进行本步骤时的基体温度在室温~500℃是优选的,更优选为150~350℃。进行本步骤时的体系(成膜腔室内)的压力1~10000Pa是优选的,更优选为10~1000Pa。
其次,从堆积反应部排出未反应的薄膜形成用原料气体或副生的气体(排气步骤)。未反应的薄膜形成用原料气体或副生的气体理想上从堆积反应部完全排气,但并无必要必定完全排气。排气方法有通过氮气、氦气、氩气等的惰性气体吹扫体系内的方法,通过使体系内减压而排气的方法,组合这些方法等。减压时的减压度为0.01~300Pa是优选的,更优选为0.01~100Pa。
其次,于堆积反应部导入氧化性气体,通过该氧化性气体的作用或氧化性气体及热的作用,从以之前的前体薄膜成膜步骤所得的前体薄膜形成金属氧化物薄膜(含有金属氧化物的薄膜形成步骤)。本步骤中,作用热时的温度在室温~500℃是优选的,更优选为150~350℃。进行本步骤时的体系(成膜腔室内)的压力优选为1~10000Pa,更优选为10~1000Pa。本发明的薄膜形成用原料与氧化性气体的反应性良好,可获得金属氧化物薄膜。
本发明的薄膜的制造方法中,采用如上述的ALD法时,将由上述的原料导入步骤、前体薄膜成膜步骤、排气步骤及含有金属氧化物的薄膜形成步骤所成的一连串操作的薄膜堆积设为1个循环,可重复复数次该循环直至获得必要膜厚的薄膜。该情况下,进行1个循环后,优选与上述排气步骤同样地,从堆积反应部排出未反应的薄膜形成用原料及反应性气体(形成金属氧化物薄膜时为氧化性气体)进而排出副生的气体后,进行下1个循环。
另外,金属氧化物薄膜的通过ALD法的形成中,也可施加等离子体、光、电压等的能量,也可使用催化剂。施加该能量时期及使用催化剂时期并未特别限定,可以为例如于原料导入步骤中的本发明的薄膜用形成用原料气体导入时、前体薄膜成膜步骤或含有金属氧化物的薄膜形成步骤中的加温时、排气步骤的体系内排气时、含有金属氧化物的薄膜形成步骤中的氧化性气体导入时,也可为上述各步骤之间。
另外,本发明的薄膜的制造方法中,薄膜堆积后,为了获得更良好的电特性,也可于惰性环境下、氧化性环境下或还原性环境下进行退火处理,于必须埋入阶差时,也可设回焊步骤。该情况的温度为200~1000℃,优选为250~500℃。
使用本发明的薄膜形成用原料制造薄膜的装置可使用周知的化学气相成长法用装置。具体的装置举例为例如图1所示的可通过冒泡供给前体而进行的装置,或如图2所示的具有气化室的装置。而且,举例为如图3及图4的可对反应性气体进行等离子体处理的装置。不限于如图1~图4的单片式装置,也可使用利用批式炉可同时处理多数片的装置。
使用本发明的薄膜形成用原料制造的薄膜,通过适当选择其他前体、反应性气体及制造条件,可成为金属、氧化物陶瓷、氮化物陶瓷、玻璃等的期望种类的薄膜。已知该薄膜显示各种电特性及光学特性等,已应用于各种用途。例如,应用于半导体、太阳能电池、TFT等的用途,其中,主要可使用作为半导体材料用的高介电材料。
[实施例]
以下列举实施例及评价例更详细说明本发明。然而,本发明不受以下实施例的任何限制。
[实施例1]利用ALD法的氧化锆薄膜的制造
将化合物No.34作为化学气相成长用原料,使用图1所示的ALD装置通过以下条件的ALD法,于形成直径220nm、深8600nm(宽高比39.1)的沟的硅基板上制造氧化锆薄膜。针对所得薄膜,利用X射线反射率法测定膜厚、利用FE-SEM的观察截面、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为3~6nm,且沟部分也以均匀的厚度形成薄膜。薄膜的组成为氧化锆(利用XPS分析由Zr3d及Ols的峰确认),而且,碳含量少于检测下限的0.1atom%。每1个循环所得的膜厚为0.02~0.04nm。
(条件)
反应温度(基板温度):210℃,反应性气体:臭氧
(步骤)
将由下述(1)~(4)所成的一连串步骤设为1个循环,重复150个循环:
(1)导入于原料容器压热温度140℃、原料容器内压力10Pa的条件气化的化学气相成长用原料的蒸气,以体系压20Pa堆积20秒;
(2)通过30秒的氩吹扫,去除未反应原料;
(3)导入反应性气体,以体系压力20Pa反应20秒;
(4)通过30秒的氩吹扫,去除未反应原料。
[比较例1]利用ALD法的氧化锆薄膜的制造
除了将下述的比较化合物1作为化学气相成长用原料以外,与以实施例1同样的条件,尝试在硅基板上制造氧化锆薄膜。对于所得到的薄膜,利用X射线反射率法测定膜厚、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为3~4nm,但沟部分以不均匀的厚度形成薄膜(在沟的底部中,是薄膜大致不形成的状态,除了在沟的底部以外,形成膜厚3~6nm的薄膜)。薄膜的组成为氧化锆(利用XPS分析,以Zr3d及Ols的峰确认),且薄膜中的碳含有量为8atom%。每1个循环所得的膜厚为0.02~0.04nm。
[化9]
比较化合物1
[比较例2]利用ALD法的氧化锆薄膜的制造
除了将下述的比较化合物2作为化学气相成长用原料以外,与以实施例1同样的条件,尝试在硅基板上制造氧化锆薄膜。对于所得到的薄膜,利用X射线反射率法测定膜厚、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为3~4nm,但沟部分以不均匀的厚度形成薄膜(在沟的底部中,是薄膜大致不形成的状态,除了在沟的底部以外,形成膜厚3~6nm的薄膜)。薄膜的组成为氧化锆(利用XPS分析,以Zr3d及Ols的峰确认),且薄膜中的碳含有量为8atom%。每1个循环所得的膜厚为0.02~0.04nm。
[化10]
比较化合物2
在实施例1中,可得到高品质的氧化锆薄膜。另外,化合物No.34的热稳定性高,可知硅基板上的宽高比高的沟的部分也可形成均匀地高品质的薄膜。另一方面,在比较例1及比较例2中,在硅基板上的宽高比高的沟的部分,不能以均匀的厚度形成薄膜,且残留于薄膜中的碳成分多,故可知不能得到高品质的氧化锆薄膜。
[实施例2]利用ALD法的氧化铪薄膜的制造
将化合物No.58作为化学气相成长用原料,使用图1所示的ALD装置通过以下条件的ALD法,于形成直径220nm、深8600nm的沟的硅基板上制造氧化铪薄膜。对所得薄膜,利用X射线反射率法测定膜厚、利用FE-SEM观察截面、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为3~6nm,且沟部分也以均匀的厚度形成薄膜。薄膜的组成为氧化铪(利用XPS分析以Hf4f及Ols的峰确认),而且,薄膜中的碳含量少于检测下限的0.1atom%。每1个循环所得的膜厚为0.02~0.04nm。
(条件)
反应温度(基板温度):280℃,反应性气体:臭氧
(步骤)
将由下述(1)~(4)所成的一连串步骤设为1个循环,重复150个循环:
(1)导入于原料容器加热温度140℃、原料容器内压力10Pa的条件气化的化学气相成长用原料的蒸气,以体系压20Pa堆积20秒;
(2)通过30秒的氩吹扫,去除未反应原料;
(3)导入反应性气体,以体系压力20Pa反应20秒;
(4)通过30秒的氩吹扫,去除未反应原料。
[实施例3]利用ALD法的氧化铪薄膜的制造
除了将化合物No.66作为化学气相成长用原料以外,与以实施例2同样的条件,在硅基板上制造氧化铪薄膜。对于所得到的薄膜,利用X射线反射率法测定膜厚、利用FE-SEM观察截面、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为3~6nm,且沟部分以均匀的厚度形成薄膜。薄膜的组成为氧化铪(利用XPS分析,以Hf4f及Ols的峰确认),且薄膜中的碳含量少于检测下限的0.1atom%。每1个循环所得的膜厚为0.02~0.04nm。
在实施例2及3中,每一个都可得到高品质的氧化铪薄膜。另外,化合物No.58及66的热稳定性高,故可知硅基板上的宽高比高的沟的部分也可形成均匀地高品质的薄膜。
需要说明的是,本国际申请主张基于2016年5月23日申请的日本国专利申请第2016-102628号的优先权,且将该日本国际申请的全内容援引加入本国际申请。
Claims (3)
1.一种薄膜形成用原料,其含有以下述通式(1)表示的化合物而成:
[化1]
式中,R1是表示碳原子数2~4的直链或分支状的烷基,R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示碳原子数1~4的烷二基,M是表示钛、锆或铪;但,M为锆时,A是碳原子数3或4的烷二基。
2.如权利要求1的薄膜形成用原料,其是ALD法用薄膜形成用原料。
3.一种薄膜的制造方法,其将含有使如权利要求1或2的薄膜形成用原料气化而得到的通式(1)表示的化合物的蒸气,导入设置有基体的成膜腔室内,使该化合物分解及/或使其进行化学反应而在该基体的表面形成含有选自钛、锆及铪中至少1种的原子的薄膜。
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CN113544309A (zh) * | 2019-03-05 | 2021-10-22 | 乔治洛德方法研究和开发液化空气有限公司 | 铟化合物以及使用该铟化合物的含铟膜成膜方法 |
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