JP2018150627A - モリブデン含有皮膜の堆積のためのビス(アルキルイミド)−ビス(アルキルアミド)モリブデン分子 - Google Patents
モリブデン含有皮膜の堆積のためのビス(アルキルイミド)−ビス(アルキルアミド)モリブデン分子 Download PDFInfo
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- JP2018150627A JP2018150627A JP2018096998A JP2018096998A JP2018150627A JP 2018150627 A JP2018150627 A JP 2018150627A JP 2018096998 A JP2018096998 A JP 2018096998A JP 2018096998 A JP2018096998 A JP 2018096998A JP 2018150627 A JP2018150627 A JP 2018150627A
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- molybdenum
- containing precursor
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- ntbu
- deposition
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 354
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 353
- 239000011733 molybdenum Substances 0.000 title claims abstract description 353
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 230000008021 deposition Effects 0.000 title claims description 47
- -1 alkyl imide Chemical class 0.000 title abstract description 5
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims description 357
- 239000000758 substrate Substances 0.000 claims description 59
- 238000000151 deposition Methods 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 27
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical group [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 4
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 abstract description 23
- 125000003368 amide group Chemical group 0.000 abstract description 8
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- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 239000007789 gas Substances 0.000 description 12
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- 125000000217 alkyl group Chemical group 0.000 description 5
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 229910052785 arsenic Inorganic materials 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 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
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
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Abstract
Description
本出願は、2013年3月15日に出願された国際出願PCT/IB2013/001038号に基づく優先権を主張する。その内容全体が引用することにより本明細書の一部をなす。
いくつかの略語、記号及び用語を以下の明細書及び特許請求の範囲全体を通して使用する。
記式中、k及びlはそれぞれ0.5〜1.5の範囲である。より好ましくは、窒化モリブデンはMo1N1であり、かつ炭化モリブデンはMo1C1である。好ましくは、酸化モリブデン及びケイ化モリブデンはMonOm及びMonSimであり、上記式中、nは0.5〜1.5の範囲であり、かつmは1.5〜3.5の範囲である。より好ましくは、酸化モリブデンはMoO2又はMoO3であり、かつケイ化モリブデンはMoSi2である。
Mo(NMe)2(NHMe)2であるモリブデン含有前駆体;
Mo(NMe)2(NHEt)2であるモリブデン含有前駆体;
Mo(NMe)2(NHPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHMe)2であるモリブデン含有前駆体;
Mo(NEt)2(NHEt)2であるモリブデン含有前駆体;
Mo(NEt)2(NHPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHsBu)2であるモリブデン含有前駆体
Mo(NSiMe3)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHtBu)2であるモリブデン含有前駆体; Mo(NMe)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NEt)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NPr)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)(NtAmyl)(NHtBu)2であるモリブデン含有前駆体;
ALDである蒸着法;
PE−ALDである蒸着法;
空間的ALDである蒸着法;
CVDである蒸着法;
PE−CVDである蒸着法;
プラズマ強化原子層堆積により基板上に堆積されたモリブデン含有前駆体の少なくとも一部;
プラズマ出力が約30W〜約600Wであり;
プラズマ出力が約100W〜約500Wであり;
モリブデン含有前駆体と還元剤とを反応させること;
N2、H2、NH3、N2H4及び任意のヒドラジン系化合物、SiH4、Si2H6、それらのラジカル種、並びにそれらの組合せからなる群から選択される還元剤;
モリブデン含有前駆体の少なくとも一部と酸化剤とを反応させること;
O2、H2O、O3、H2O2、N2O、NO、酢酸、それらのラジカル種、及びそれらの組合せからなる群から選択される酸化剤;
約0.01Pa〜約1×105Paの圧力で上記方法を行うこと;
約0.1Pa〜約1×104Paの圧力で上記方法を行うこと;
約20℃〜約500℃の温度で上記方法を行うこと;
約330℃〜約500℃の温度で上記方法を行うこと;
Moであるモリブデン含有皮膜;
MoOであるモリブデン含有皮膜;
MoNであるモリブデン含有皮膜;
MoSiであるモリブデン含有皮膜;
MoSiNであるモリブデン含有皮膜;及び、
MoCNであるモリブデン含有皮膜。
Mo(NMe)2(NHMe)2であるモリブデン含有前駆体;
Mo(NMe)2(NHEt)2であるモリブデン含有前駆体;
Mo(NMe)2(NHPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHMe)2であるモリブデン含有前駆体;
Mo(NEt)2(NHEt)2であるモリブデン含有前駆体;
Mo(NEt)2(NHPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHsBu)2であるモリブデン含有前駆体
Mo(NiPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHsBu)2であるモリブデン含有前駆体
Mo(NSiMe3)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHtBu)2であるモリブデン含有前駆体; Mo(NMe)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NEt)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NPr)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)(NtAmyl)(NHtBu)2であるモリブデン含有前駆体;
プラズマ強化化学蒸着法である化学蒸着法;
プラズマ出力が約30W〜約600Wであり;
プラズマ出力が約100W〜約500Wであり;
O2、H2O、O3、H2O2、N2O、NO、酢酸、それらのラジカル種、及びそれらの組合せからなる群から選択される酸化剤;
約0.01Pa〜約1×105Paの圧力で上記方法を行うこと;
約0.1Pa〜約1×104Paの圧力で上記方法を行うこと;
約20℃〜約500℃の温度で上記方法を行うこと;
約330℃〜約500℃の温度で上記方法を行うこと。
を含み得る:
Mo(NMe)2(NHMe)2であるモリブデン含有前駆体;
Mo(NMe)2(NHEt)2であるモリブデン含有前駆体;
Mo(NMe)2(NHPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NMe)2(NHBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NMe)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHMe)2であるモリブデン含有前駆体;
Mo(NEt)2(NHEt)2であるモリブデン含有前駆体;
Mo(NEt)2(NHPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NEt)2(NHBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NEt)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NiPr)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NiBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NsBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NSiMe3)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHMe)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHEt)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NCF3)2(NHtBu)2であるモリブデン含有前駆体; Mo(NMe)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NEt)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NPr)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHMe)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHEt)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiPr)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHiBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHsBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHtBu)2であるモリブデン含有前駆体;
Mo(NtAmyl)2(NHSiMe3)2であるモリブデン含有前駆体;
Mo(NtBu)(NtAmyl)(NHtBu)2であるモリブデン含有前駆体;
プラズマ強化原子層堆積により基板上に堆積されたモリブデン含有前駆体の少なくとも一部;
プラズマ出力が約30W〜約600Wであり;
プラズマ出力が約100W〜約500Wであり;
モリブデン含有前駆体と還元剤とを反応させること;
N2、H2、NH3、N2H4及び任意のヒドラジン系化合物、SiH4、Si2H6、それらのラジカル種、並びにそれらの組合せからなる群から選択される還元剤;
モリブデン含有前駆体の少なくとも一部と酸化剤とを反応させること;
O2、H2O、O3、H2O2、N2O、NO、酢酸、それらのラジカル種、及びそれらの組合せからなる群から選択される酸化剤;
約0.01Pa〜約1×105Paの圧力で上記方法を行うこと;
約0.1Pa〜約1×104Paの圧力で上記方法を行うこと;
約20℃〜約500℃の温度で上記方法を行うこと;
約330℃〜約500℃の温度で上記方法を行うこと;
Moであるモリブデン含有皮膜;
MoOであるモリブデン含有皮膜;
MoNであるモリブデン含有皮膜;
MoSiであるモリブデン含有皮膜;
MoSiNであるモリブデン含有皮膜;及び、
MoCNであるモリブデン含有皮膜。
記ビス(アルキルイミド)−ビス(アルキルアミド)モリブデン化合物は、式Mo(NR)2(NHR’)2(式中、R及びR’は、独立してC1〜C4アルキル基、C1〜C4ペルフルオロアルキル基及びアルキルシリル基からなる群から選択される)を有する。
反応性を高めることができ、こうしてより良好な皮膜密度と、MoN皮膜については、より低いC及びOの濃度と、MoO皮膜については、より低いC及びNの濃度が得られる。上記MoN皮膜のより高い密度は、該皮膜のバリア性を高めるであろう。MoO皮膜の堆積の場合に、より高いALD温度域は、より高いκ値をもたらすより良好な結晶学的相の堆積を可能にする。
つかの実施形態では、基板はMIM、DRAM若しくはFeRam技術において誘電材料として使用される酸化物(例えば、ZrO2系材料、HfO2系材料、TiO2系材料、希土類酸化物系材料、三元酸化物系材料等)から又は銅と低k層との間の酸素障壁として使用される窒化物系層(例えばTaN)から選ぶことができる。他の基板を半導体、光起電装置、LCD−TFT又はフラットパネルデバイスの製造に使用してもよい。このような基板の例としては、銅及びCuMnのような銅系合金、金属窒化物含有基板(例えば、TaN、TiN、WN、TaCN、TiCN、TaSiN及びTiSiN);絶縁体(例えば、SiO2、Si3N4、SiON、HfO2、Ta2O5、ZrO2、TiO2、Al2O3及びチタン酸バリウムストロンチウム);又はこれらの材料のあらゆる数の組合せを含む他の基板等の固体基板が挙げられるが、これらに限定されない。例えば、ポリ(3,4−エチレンジオキシチオフェン)ポリ(スチレンスルホン酸)[PEDOT:PSS]のようなプラスチック基板を使用することができる。用いられる実際の基板は、用いられる特定の化合物の実施形態によっても変わり得る。しかし、多くの例では、用いられる好ましい基板は、Si及びSiO2基板から選択される。
H6、Si3H8、(Me)2SiH2、(C2H5)2SiH2、(CH3)3SiH、(C2H5)3SiH、[N(C2H5)2]2SiH2、N(CH3)3、N(C2H5)3、(SiMe3)2NH、(CH3)HNNH2、(CH3)2NNH2、フェニルヒドラジン、B2H6、(SiH3)3N、これらの還元剤のラジカル種及びこれらの還元剤の混合物から選択される還元剤を含み得る。ALDプロセスが行われる場合には、上記還元試薬はH2であることが好ましい。
ャンバ中に通過させる前に処理してよい。2.45GHz、7kWのプラズマ出力及びおよそ3Torrからおよそ10Torrまでの範囲の圧力で作動させると、反応ガスO2は、2つのO−ラジカルへと分解され得る。好ましくは、リモートプラズマは、約1kWから約10kWまでの範囲の、より好ましくは約2.5kWから約7.5kWまでの範囲の出力で発生させることができる。
ッシュアニーリングプロセスを別の装置で行ってもよい。上記後処理法のいずれか、特に熱的アニーリングは、上記モリブデン含有皮膜の任意の炭素及び窒素の混入を効率的に減らすことが予想される。これはまた、上記皮膜の抵抗率を向上させることが予想される。後処理後のMoN皮膜の抵抗率は、およそ50μΩ・cm−1〜1000μΩ・cm−1の範囲であってよい。
for the fabrication of ultra-shallow junctions)、Surface Coatings Technology, 156 (1-3) 2002, pp. 229-236を参照のこと)。そのドーピング法はその全体が引用することにより本明細書の一部をなす。
Mo(NtBu)2(NHtBu)2を、共反応物としてアンモニアを使用するALD方式でのMoN皮膜の堆積のために使用した。上記モリブデン分子は、キャニスター中に保管し、80℃で加熱し、そして蒸気はN2又はArバブリング法によって反応炉へと供給する。導管は、反応物の凝縮を避けるために100℃に加熱する。送出構成は、モリブデン前駆体の蒸気とアンモニアとの交互の導入を可能にする。窒化モリブデン皮膜は、425℃において約1.3Å/サイクルの堆積速度で得られる(図2)。この温度を上回ると、堆積速度は劇的に増大する。それは、Mo(NtBu)2(NHtBu)2がこの温度を上回ると熱的自己分解を起こすことの証拠かもしれない。
約10原子%である。Oの濃度は約8原子%である。これらの低い濃度は、該皮膜の良好な品質を示している。上記皮膜の良好な品質は、更に、該MoN皮膜の低い抵抗率によって確認された。上記MoN皮膜の抵抗率は、広い堆積温度域にわたり測定された(図7)。堆積温度がより高いと、該皮膜の抵抗率がより低くなることが観察される。この結果は、高温ALDプロセスの利益が、本明細書に記載される一群の安定な分子の使用により可能になったことを立証している。
Miikkulainenらは、Chem. Vap. Deposition ((2008) 14, 71-77)において、NH3とMo(NtBu)2(NMe2)2又はMo(NtBu)2(NEt2)2とからのMoNのALD堆積の結果を開示している。Miikkulainenらは、ALDがMo(NtBu)2(NiPr2)2ではその熱的不安定性のため不適切であると開示している(同上書第72頁)。Miikkulainenらは、Mo(NtBu)2(NEt2)2についての堆積試験結果が、Mo(NtBu)2(NMe2)2について以前に報告されていた結果と同様であり、両者とも300℃の最高成長温度と0.5Å/サイクルの成長速度を示すことを報告している(同上書第73頁)。更に、Mo(NtBu)2(NMe2)2及びMo(NtBu)2(NEt2)2の堆積によって作製されたMoN皮膜は、同様の元素組成:Mo37%、N41%、C8%、O14%を有する(同上書第74頁〜第75頁)。
実施例1と同じ前駆体が使用されるが、NH3はオゾン(O3)と置き換える。同じALD導入スキームを使用する。飽和は400℃で得られると予想される。組成分析により、得られた皮膜がMoO2、MoO3又はMoxOy(式中、x及びyは、1〜5から選択される)であることと、該皮膜中の炭素含量が低い(0〜2原子%)こととが確認されると予想される。H2/N2混合物雰囲気下での500℃での10分間にわたるアニーリングの後の酸化モリブデン層は、MoO2であると予想される。
実施例1と同じ前駆体をNH3と一緒に使用し、ALD方式のスキームにおいて反応チャンバーに供給した。この場合に、200Wの直接プラズマ源は、NH3パルスの間にスイッチを入れた。窒化モリブデン皮膜は、450℃まで約1.0Å/サイクルの堆積速度で得られた(図8)。プラズマ源の使用は、炭素及び酸素という不純物の濃度を約2%未満にまで下げることを可能にした(図9)。上記MoN皮膜の抵抗率を、広い堆積温度域にわたり測定した(図10)。そして該皮膜中の低い不純物の結果として、抵抗率もまた612μΩ・cmほど低下される。
ら逸脱することなく当業者が行うことができる。本明細書中に記載される実施形態は例示的なものにすぎず、限定的なものではない。組成物及び方法の多くの変形及び修正が可能であり、本発明の範囲内である。それ故、保護範囲は本明細書中に記載される実施形態に限定されず、添付の特許請求の範囲によってのみ限定されるものであり、その範囲は、特許請求の範囲の主題のあらゆる均等物を含むものとする。
Claims (9)
- モリブデン含有皮膜を基板上に形成する原子層堆積法であって、
式Mo(NtBu)2(NHtBu)2で表されるモリブデン含有前駆体を、基板を収容した蒸着チャンバ中に導入することと、
前記モリブデン含有前駆体を前記基板に接触させることと、
還元剤を前記蒸着チャンバ中に導入して前記モリブデン含有皮膜を形成することと、
を含む、原子層堆積法。 - 前記還元剤は、N2、H2、NH3、SiH4、Si2H6、(Me)2SiH2、(C2H5)2SiH2、(CH3)3SiH、(C2H5)3SiH、[N(C2H5)2]2SiH2、N(CH3)3、N(C2H5)3、(SiMe3)2NH、(CH3)HNNH2、(CH3)2NNH2、フェニルヒドラジン、B2H6、(SiH3)3N、これらの還元剤のラジカル種及びこれらの還元剤の混合物から選択される、請求項1に記載の原子層堆積法。
- 前記還元剤は、NH3である、請求項2に記載の原子層堆積法。
- 前記還元剤をプラズマ処理することをさらに含む、請求項1〜3のいずれか1項に記載の原子層堆積法。
- 前記蒸着チャンバ内の温度を330℃〜450℃の間の温度に維持することを含む、請求項1〜4のいずれか1項に記載の原子層堆積法。
- 前記モリブデン含有皮膜が、窒化モリブデンである、請求項1〜4のいずれか1項に記載の原子層堆積法。
- 前記窒化モリブデン皮膜は、炭素及び酸素の不純物を2%未満含む、請求項6に記載の原子層堆積法。
- 炭素及び酸素の不純物を2%未満含む窒化モリブデン皮膜を堆積させる原子層堆積プロセスであって、
式Mo(NtBu)2(NHtBu)2で表されるモリブデン含有前駆体を、基板を収容した蒸着チャンバ中に導入することと、
前記モリブデン含有前駆体を前記基板に接触させることと、
プラズマにより活性化されたNH3を前記蒸着チャンバ中に導入して前記窒化モリブデン皮膜を形成することと、
を含む、原子層堆積法。 - 前記蒸着チャンバ内の温度を330℃〜450℃の間の温度に維持することを含む、請求項8に記載の原子層堆積法。
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JP2011523503A (ja) * | 2008-05-01 | 2011-08-11 | オヴォニクス,インコーポレイテッド | 相変化メモリデバイスに電極を形成する気相法 |
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US5064686A (en) * | 1990-10-29 | 1991-11-12 | Olin Corporation | Sub-valent molybdenum, tungsten, and chromium amides as sources for thermal chemical vapor deposition of metal-containing films |
US6114242A (en) * | 1997-12-05 | 2000-09-05 | Taiwan Semiconductor Manufacturing Company | MOCVD molybdenum nitride diffusion barrier for Cu metallization |
US6835671B2 (en) | 2002-08-16 | 2004-12-28 | Freescale Semiconductor, Inc. | Method of making an integrated circuit using an EUV mask formed by atomic layer deposition |
EP2029790A1 (en) * | 2006-06-02 | 2009-03-04 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing |
WO2010114386A1 (en) * | 2009-03-30 | 2010-10-07 | Universitetet I Oslo | Thin films containing molybdenum oxide |
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KR101627988B1 (ko) | 2016-06-07 |
TWI596099B (zh) | 2017-08-21 |
JP2016516892A (ja) | 2016-06-09 |
KR20150126857A (ko) | 2015-11-13 |
TW201504247A (zh) | 2015-02-01 |
US20160002786A1 (en) | 2016-01-07 |
WO2014140863A2 (en) | 2014-09-18 |
SG11201507672QA (en) | 2015-10-29 |
WO2014140863A3 (en) | 2015-01-29 |
WO2014140672A1 (en) | 2014-09-18 |
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