CN102947482A - 用于cvd和ald的含钌前体 - Google Patents
用于cvd和ald的含钌前体 Download PDFInfo
- Publication number
- CN102947482A CN102947482A CN2011800300424A CN201180030042A CN102947482A CN 102947482 A CN102947482 A CN 102947482A CN 2011800300424 A CN2011800300424 A CN 2011800300424A CN 201180030042 A CN201180030042 A CN 201180030042A CN 102947482 A CN102947482 A CN 102947482A
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- Prior art keywords
- cyclohexadiene
- methyl
- reaction chamber
- precursor
- propyl
- Prior art date
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- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 41
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 title abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 30
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 30
- 239000000376 reactant Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000005137 deposition process Methods 0.000 claims description 14
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- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 6
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- UBIXBJDZNKCENM-UHFFFAOYSA-N 1-ethyl-4-methylcyclohexa-1,3-diene Chemical compound CCC1=CC=C(C)CC1 UBIXBJDZNKCENM-UHFFFAOYSA-N 0.000 claims description 4
- KOOLEOYFSBWOQQ-UHFFFAOYSA-N 1-ethyl-5-methylcyclohexa-1,4-diene Chemical compound CCC1=CCC=C(C)C1 KOOLEOYFSBWOQQ-UHFFFAOYSA-N 0.000 claims description 4
- QDSVHUIXOBBMCW-UHFFFAOYSA-N 1-methyl-4-propylcyclohexa-1,3-diene Chemical compound CCCC1=CC=C(C)CC1 QDSVHUIXOBBMCW-UHFFFAOYSA-N 0.000 claims description 4
- JOYLQRQNHGASBI-UHFFFAOYSA-N 1-methyl-5-propylcyclohexa-1,4-diene Chemical compound CCCC1=CCC=C(C)C1 JOYLQRQNHGASBI-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
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- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- TYMUFQXLPNZKGZ-UHFFFAOYSA-N 1,5-dimethylcyclohexa-1,4-diene Chemical compound CC1=CCC=C(C)C1 TYMUFQXLPNZKGZ-UHFFFAOYSA-N 0.000 claims description 3
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 238000005019 vapor deposition process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
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- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- 239000012159 carrier gas Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
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- 238000000231 atomic layer deposition Methods 0.000 description 3
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- 229910052718 tin Inorganic materials 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910004121 SrRuO Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
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- 229910019001 CoSi Inorganic materials 0.000 description 1
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910005881 NiSi 2 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
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- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
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- NMGSDTSOSIPXTN-UHFFFAOYSA-N cyclohexa-1,2-diene Chemical compound C1CC=C=CC1 NMGSDTSOSIPXTN-UHFFFAOYSA-N 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C23C16/22—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
- C23C16/06—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
- C23C16/06—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
- C23C16/16—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 metal carbonyl 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
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Abstract
本发明公开了含钌前体和在CVD和ALD中使用该含钌前体的方法。所公开的前体是具有通式[L]mRu(CO)3的金属三羰基络合物,其中L是直链或支链不饱和烃或具有两个或更多个取代基的环状不饱和烃;且m是1或2。
Description
对相关申请的交叉引用
本申请要求2010年12月30日提交的美国非临时申请No.12/981,798的权益,其要求2010年4月19日提交的美国临时申请No.61/325,487的权益,其整个内容经此引用并入本文。
技术领域
本发明公开了含钌前体和在CVD和ALD中使用该含钌前体的方法。
背景技术
钌膜和含钌膜,例如SrRuO和RuO2,已用于半导体器件(例如金属电极和Cu晶种层)中的若干部件。钌的电阻率低于Ir和Pt。另外,RuO2的电导率优于两种相应的Ir和Pt金属氧化物,这在沉积的金属层在后继工艺过程中与氧化剂(例如O2、O3)接触时是重要的。随着芯片尺寸变小,各层必须更薄。因此需要化学气相沉积(CVD)和优选原子层沉积(ALD)技术,还需要可用于CVD和ALD模式的前体。
可获得多种多样的钌络合物,一些已在CVD或ALD模式中研究。但是,其中大多数具有缺点,例如低蒸气压和/或沉积表现出高杂质含量(在大多数情况下为C和O)、长培养时间、差的粘附性和在深槽中的不均匀性的薄膜。此外,一些前体不是液体,并需要溶解在溶剂或溶剂混合物中才能使蒸气易输送到反应室中。
三羰基钌产物被报道为CVD/ALD前体(参见例如美国专利Nos.6,517,616和6,897,160和JP2002-212112)。PCT公开No.WO2008/034468公开了(Rn-CHD)Ru(CO)3前体,其中R选自C1-C4直链或支链烷基、烷基酰胺、烷氧基、烷基甲硅烷基酰胺、脒基、羰基和/或氟烷基取代基且n可以为1至8。
仍然需要具有适合气相沉积的性质的含钌前体。
标记法和命名法
在下列说明书和权利要求中使用某些缩写、符号和术语并包括:术语“不饱和烃”是指仅含碳和氢原子的不饱和官能团。此外,术语“不饱和烃”是指直链、支链或环状不饱和烃基团。直链不饱和烃基团的实例包括但不限于,乙烯基团、丙烯基团、丁烯基团等。支链不饱和烃基团的实例包括但不限于,2-甲基-2,4-戊二烯。环状不饱和烃基的实例包括但不限于,环己二烯基等。
缩写“Me”是指甲基;缩写“Et”是指乙基;缩写“Pr”是指丙基;缩写“iPr”是指异丙基;缩写“Bu”是指丁基(正丁基);缩写“tBu”是指叔丁基;缩写“sBu”是指仲丁基;且缩写“CHD”是指环己二烯基。
在本文中使用来自元素周期表的元素的标准缩写。应该理解的是,可以通过这些缩写提到元素(例如Ru是指钌,Sr是指锶,等等)。
发明概要
本发明公开了在基底上形成含钌层的方法。提供反应室,该反应室具有至少一个位于其内的基底。将蒸气引入反应室。该蒸气包含至少一种具有式[L]mRu(CO)3的化合物;其中L是直链或支链不饱和烃或具有两个或更多个取代基的环状不饱和烃,且m是1或2。使所述蒸气与基底接触,以使用气相沉积法在基底的至少一个表面上形成含钌层。该方法可进一步包括下述方面的一个或多个:
·所述气相沉积法是CVD和/或ALD;
·所述至少一种化合物选自Ru(乙烯)2(CO)3、Ru(丙烯)2(CO)3、Ru(丁烯)2(CO)3;
·所述至少一种化合物选自Ru(2,4-戊二烯)(CO)3、Ru(2-甲基-2,4-戊二烯)(CO)3、Ru(1,4-戊二烯)(CO)3、Ru(2,4-己二烯)(CO)3、Ru(2,4-己二烯醛)(CO)3、Ru(2,4-庚二烯)(CO)3、Ru(1,4-二甲基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-乙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-正丙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3、Ru(1,5-二甲基-1,4-环己二烯)(CO)3、Ru(1-甲基-5-乙基-1,4-环己二烯)(CO)3、Ru(1-甲基-5-正丙基-1,4-环己二烯)(CO)3和Ru(1-甲基-5-异丙基-1,4-环己二烯)(CO)3;
·L是“C=C-C=C”或“C=C-CH2-C=C”;
·所述至少一种化合物在大约-20℃至大约100℃的温度是液体;
·所述至少一种化合物在大约-20℃至大约30℃的温度是液体;
·所述至少一种化合物在大约-20℃至大约0℃的温度是液体;
·所述气相沉积法是热气相沉积法或等离子体气相沉积法;
·所述反应室含有1至200个晶片;
·所述气相沉积法在大约0.01Torr(1.33Pa)至大约1000Torr(133,322Pa)的压力范围内进行;
·所述气相沉积法在大约0.1Torr(13.3Pa)至大约100Torr(13,332.2Pa)的压力范围内进行;
·所述气相沉积法在大约10℃至大约400℃的温度范围内进行;
·所述气相沉积法在大约25℃至大约350℃的温度范围内进行;
·所述气相沉积法在大约50℃至大约300℃的温度范围内进行;
·将反应物引入反应室;
·所述反应物选自氢(H2)、氨(NH3)、硅烷(SiH4)、二乙基硅烷(SiEt2H2)、它们的受激物类及其混合物;和
·所述反应物选自氧(O2)、水(H2O)、臭氧(O3)、H2O2、NO、NO2、羧酸(RCOOH)、它们的受激物类及其混合物。
附图简述
为了进一步理解本发明的性质和目的,应参考联系附图考虑的下列详述,其中:
图1是显示Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3的质量损失百分比与温度的关系的热重分析(TGA)图;且
图2是Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3的蒸气压与温度的关系的图。
优选实施方案详述
本发明公开了含钌前体。所公开的前体可以是热稳定(在输递条件下)的,以便以高反应性用在CVD和ALD沉积中。
所公开的前体是具有通式LmRu(CO)3的金属三羰基络合物,其中L是具有两个或更多个取代基的直链或支链不饱和烃或环状不饱和烃;且m是1或2。
在一个实施方案中,所公开的前体具有式L2Ru(CO)3且L是直链不饱和烃,例如乙烯、丙烯或丁烯。示例性前体包括Ru(乙烯)2(CO)3、Ru(丙烯)2(CO)3和Ru(丁烯)2(CO)3。
在另一实施方案中,所公开的前体具有式LRu(CO)3且L如下所示与Ru原子键合:
在此实施方案中,L可以是2,4-戊二烯、2-甲基-2,4-戊二烯、1,4-戊二烯、2,4-己二烯、2,4-己二烯醛、2,4-庚二烯。或者,L可以是具有2个或更多个取代基的环己二烯分子,例如1,4-二甲基-1,3-环己二烯、1-甲基-4-乙基-1,3-环己二烯、1-甲基-4-正丙基-1,3-环己二烯、1-甲基-4-异丙基-1,3-环己二烯、1-甲基-5-甲基-1,4-环己二烯、1-甲基-5-乙基-1,4-环己二烯、1-甲基-5-正丙基-1,4-环己二烯、1-甲基-5-异丙基-1,4-环己二烯。示例性前体包括Ru(2,4-戊二烯)(CO)3、Ru(2-甲基-2,4-戊二烯)(CO)3、Ru(1,4-戊二烯)(CO)3、Ru(2,4-己二烯)(CO)3、Ru(2,4-己二烯醛)(CO)3、Ru(2,4-庚二烯)(CO)3、Ru(1,4-二甲基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-乙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-正丙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3、Ru(1,5-二甲基-1,4-环己二烯)(CO)3、Ru(1-甲基-5-乙基-1,4-环己二烯)(CO)3和Ru(1-甲基-5-正丙基-1,4-环己二烯)(CO)3。所述前体优选是Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3。
所公开的前体优选在大约-20℃至大约100℃、更优选大约-20℃至大约30℃、再更优选大约-20℃至大约0℃的温度是液体。
配体选择
一些LmRu(CO)3化合物表现出适用于CVD/ALD沉积的性质。L配体的选择基于所得含钌层的预期用途。但是,钌原子的氧化态和配体L的位阻并非总是相同,并一些结构可能不能制成。
例如,当L不是中性配体(例如取代的环戊二烯)时,LmRu(CO)3化合物中的钌的氧化态不是0,以产生稳定的LmRu(CO)3化合物。在这些情况下,在CVD或ALD法中需要氧,以使Ru原子与非中性L配体之间的键断裂。因此,所得含钌层还可能含有氧。
但是,当L是中性配体(例如二烯(m=1)或不饱和烃(m=1或2))时,LmRu(CO)3化合物中的钌的氧化态是0。在这种情况下,氧或臭氧不是键断裂所必需的。可以使用氢代替氧。所得含Ru层可用于无法使用氧的一些部件,例如阻挡层。
活性位点
除上述配体选择外,一些配体不能制造LmRu(CO)3结构。配体分子L可以是“C(1)=C(2)-C(3)=C(4)”或“C(5)=C(6)-C(7)H2-C(8)=C(9)”。在二烯分子的情况下,两个双键应更靠近且C(2)、(3)、(6)、(8)在碳上不应具有取代基(除氢外)。换言之,1,3-二烯分子优于1,4-二烯分子。
另外,C(2)、(3)、(6)或(8)碳分子上的任何非氢取代基可能阻碍LmM(CO)3分子形成。为避免位阻,该配体分子可能需要“开放位点”以产生tbp(三角双锥形)结构。例如,当配体没有活性位点,例如L=1-甲基-4-异丙基-1,4-环己二烯或1,3,5-三甲基-1,4-环己二烯时,不获得LM(CO)3产物。
沉积方法
所公开的前体可用于使用气相沉积法在一个或多个基底(例如半导体基底或基底组装件)上形成含钌层。该方法可用于制造半导体、光电器件、LCD-TFT和平板器件。该方法包括:提供基底;提供包含至少一种含钌前体的蒸气;和使所述包含含钌前体的蒸气与基底接触(和通常将蒸气引向基底);和向基底提供还原剂或氧化剂的蒸气,以在基底的至少一个表面上形成含钌层。
可以使用本领域技术人员已知的任何沉积方法使所公开的前体化合物沉积,以形成含钌膜。合适的沉积方法的实例包括但不限于,常规化学气相沉积(CVD)、等离子体增强的化学气相沉积(PECVD)、低压化学气相沉积(LPCVD)、原子层沉积(ALD)、脉冲化学气相沉积(P-CVD)、等离子体增强的原子层沉积(PE-ALD)、它们的组合和/或本领域技术人员已知的任何其它沉积技术。该沉积方法优选是热气相沉积法或等离子体气相沉积法。该沉积方法更优选是ALD或PE-ALD。
将前体的蒸气引入含有至少一个基底的反应室。该反应室可含有1至200个晶片。反应室可以是在其中进行沉积法的装置的任何封闭空间或室,例如但不限于,平行板型反应器、冷壁型反应器、热壁型反应器、单晶片反应器、多晶片反应器或其它这样类型的沉积系统。
反应室内的温度和压力和基底的温度保持在合适的条件下,以使含钌前体的蒸气与基底之间的接触导致在基底的至少一个表面上形成含Ru层。也可以使用反应物以助于形成含Ru层。
该反应室可以保持在大约0.01Torr(1.33Pa)至大约1000Torr(133,322Pa)、更优选大约0.1Torr(13.3Pa)至大约100Torr(13,332.2Pa)的压力。反应室内的温度可以为大约10℃至大约100℃,优选大约25℃至大约350℃,更优选大约50℃至大约300℃。本领域普通技术人员会认识到,可通过单纯的实验优化温度以实现所需结果。
在其上沉积含钌膜的基底的类型随最终预期用途而变。在一些实施方案中,基底可选自用作MIM、DRAM、FeRam技术中的介电材料或CMOS技术中的栅极电介质的氧化物(例如RuO2基材料、三元氧化物基材料等),或选自用作铜与低k层之间的隔氧层的氮化物基的膜(例如RuN)。在半导体、光伏器件、LCD-TFT或平板器件的制造中可以使用其它基底。这样的基底的实例包括,但不限于,固体基底,例如金属基底(例如Au、Pd、Rh、Ru、W、Al、Ni、Ti、Co、Pt,和金属硅化物,例如TiSi2、CoSi2和NiSi2);含金属氮化物的基底(例如TaN、TiN、TiAlN、WN、TaCN、TiCN、TaSiN和TiSiN);半导体材料(例如Si、SiGe、GaAs、InP、金刚石、GaN和SiC);绝缘体(例如SiO2、Si3N4、SiON、HfO2、Ta2O5、ZrO2、TiO2、Al2O3和钛酸钡锶);或包括这些材料的许多组合的其它基底。所用实际基底也可能取决于所用的特定前体实施方案。但在许多情况下,所用的优选基底选自TiN、Ru和Si型基底。
可以将基底加热至足以以充足生长速率和以所需物理状态和组成获得所需钌或含钌膜的温度。可将基底加热达到的非限制性的示例性温度范围包括150℃至600℃。基底温度优选保持低于或等于450℃。
可以在将前体引入反应室之前以液态将其送入汽化器中,在此将其汽化。在其汽化之前,可任选地将前体与一种或多种溶剂、一种或多种金属源、以及一种或多种溶剂和一种或多种金属源的混合物混合。所述溶剂可选自甲苯、乙基苯、二甲苯、均三甲苯、癸烷、十二烷、辛烷、己烷、戊烷等。所得浓度可以为大约0.05M至大约2M。金属源可包括现在已知或以后开发的任何金属前体。
或者,可以通过使载气通过含前体的容器或通过将载气鼓泡加入前体来将前体汽化。然后将载气和前体以蒸气形式引入反应室。载气可包括,但不限于,Ar、He、N2及其混合物。可任选地将前体在容器中与溶剂、另一金属前体或其混合物混合。如果必要,可以将该容器加热至允许前体呈其液相并具有充足蒸气压的温度。可将该容器保持在例如0-150℃的温度。本领域技术人员认识到,可以以已知方式调节该容器的温度以控制汽化的前体的量。
除了在引入反应室之前该前体与溶剂、金属前体和稳定剂的任选混合之外,还可以将前体与反应物在反应室内混合。示例性的反应物包括,但不限于,H2、含氢流体、醇(ROH,R是C1-C6烷基)、金属前体(例如含锶前体、含钡前体、含铝前体,如TMA)和它们的任何组合。
当所需含钌膜还含有氧时,例如且不限于RuO2,反应物可包括氧源,其选自但不限于O2、O3、H2O、H2O2、乙酸、福尔马林、低聚甲醛及其组合。
当所需含钌膜还含有氮时,例如且不限于氮化钌,反应物可包括氮源,其选自但不限于氮(N2)、氨及其烷基衍生物、亚胺、肼及其烷基衍生物、含N的自由基(例如N·、NH·、NH2 ·)、NO、N2O、NO2、胺和它们的任何组合。
当所需含钌膜还含有碳时,例如且不限于碳化钌,反应物可包括碳源,其选自但不限于甲烷、乙烷、丙烷、丁烷、乙烯、丙烯、叔丁烯、异丁烯、CCl4和它们的任何组合。
当所需含钌膜还含有硅时,例如且不限于硅化钌或硅酸钌,反应物可包括硅源,其选自但不限于SiH4、Si2H6、Si3H8、TriDMAS、BDMAS、BDEAS、TDEAS、TDMAS、TEMAS、(SiH3)3N、(SiH3)2O、三甲硅烷基胺、二硅氧烷、三甲硅烷基胺、二硅烷、三硅烷、烷氧基硅烷SiHx(OR1)4-x、硅烷醇Si(OH)x(OR1)4-x(优选地Si(OH)(OR1)3;更优选Si(OH)(OtBu)3、氨基硅烷SiHx(NR1R2)4-x(其中x是1、2、3或4;R1和R2独立地为H或直链、支链或环状C1-C6碳链;优选TriDMAS、BTBAS和/或BDEAS)和它们的任何组合。或者,目标薄膜可含有锗(Ge),在这种情况下可以将上述含Si反应物换成含Ge反应物。
当所需含钌膜还含有另一金属时,例如且不限于B、In、Zn、Au、Pd、Ag、Ti、Ta、Hf、Zr、Nb、Mg、Al、Sr、Y、Ba、Ca、As、Sb、Bi、Sn、Pb或其组合,反应物可包括含金属的第二前体。第二前体可选自但不限于烷基金属,例如B2H6、SbRi’ 3或SnRi’ 4(其中各Ri”独立地为H或直链、支链或环状C1-C6碳链)、金属醇盐,例如Sb(ORi)3或Sn(ORi)4(其中各Ri独立地为H或直链、支链或环状C1-C6碳链)和金属胺,例如Sb(NR1R2)(NR3R4)(NR5R6)或Ge(NR1R2)(NR3R4)(NR5R6)(NR7R8)(其中各R1、R2、R3、R4、R5、R6、R7和R8独立地为H、C1-C6碳链或三烷基甲硅烷基,该碳链和三烷基甲硅烷基各自是直链、支链或环状的)和它们的任何组合。
在一个优选实施方案中,反应物可选自但不限于氢(H2)、氨(NH3)、硅烷(SiH4)、二乙基硅烷(SiEt2H2)、它们的受激物类及其混合物。在另一优选实施方案中,反应物可选自但不限于氧(O2)、水(H2O)、臭氧(O3)、H2O2、NO、NO2、羧酸(RCOOH)、它们的受激物类及其混合物。
可以将前体和一种或多种反应物同时(化学气相沉积)、相继(原子层沉积)或以其它组合引入反应室。例如,前体可以在一个脉冲中引入且两种附加金属源可以在分开的脉冲中一起引入[改性原子层沉积]。或者,反应室在前体引入之前已含有反应物。可以使反应物经过远离反应室的等离子体系统并分解成自由基。或者,可以将前体连续引入反应室,同时通过脉冲引入其它金属源(脉冲化学气相沉积)。在各实例中,在脉冲后接着吹扫或排空步骤以除去引入的过量组分。在各实例中,脉冲可持续大约0.01s至大约10s、或大约0.3s至大约3s、或大约0.5s至大约2s的时期。
在一个非限制性示例性原子层沉积型方法中,将所公开的前体的气相引入反应室,在此使其与合适的基底接触。然后通过吹扫和/或排空反应器从反应室中除去过量前体。将氧源引入反应室,在此其以自限方式与吸收的前体反应。通过吹扫和/或排空反应室从反应室中除去任何过量氧源。如果所需膜是氧化钌膜,这种两步法可提供所需薄膜厚度,或可重复直至获得具有必要厚度的薄膜。
或者,如果所需膜是钌金属氧化物膜,在上述两步法后可以将金属前体蒸气引入反应室中。根据沉积的钌金属氧化物的性质选择金属前体。在引入反应室后,使该金属前体与基底接触。然后通过吹扫和/或排空反应室从反应室中除去任何过量金属前体。同样,可以将氧源引入反应室以与所述第二金属前体反应。通过吹扫和/或排空反应室从反应室中除去过量氧源。如果达到所需薄膜厚度,可终止该方法。但是,如果需要较厚薄膜,可以重复整个四步法。通过交替提供前体、金属前体和氧源,可以沉积具有所需组成和厚度的薄膜。
由上述方法制成的含钌膜或层可包括SrRuO和RuO2。本领域普通技术人员会认识到,通过合理选择适当的前体和反应物,可以获得所需膜组成。
实施例
提供下述非限制性实施例以进一步例示本发明的实施方案。但是,该实施例不是为了包含一切,并且不是为了限制本文所述的本发明的范围。
Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)
3
的合成
将Ru3(CO)12(10克,15.6毫摩尔)与1-甲基-4-异丙基-1,3-环己二烯(25毫升,0.15摩尔)在200毫升甲苯中在回流下混合17小时。在反应后,在真空压力下除去过量溶剂和配体分子。将剩余液体在真空压力下蒸馏两次并获得浅黄色液体(70℃/20mmHg)作为最终产物(收率约82%)。作为另一提纯法,通过柱色谱法(硅胶,溶剂己烷)分离产物。收集浅黄色级分(Rf=0.7)并在真空压力下在室温下除去溶剂。
图1是显示Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3的质量损失百分比与温度的关系的热重分析(TGA)图。TGA结果表明在20Torr下的良好蒸发,没有任何残留。
图2是Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3的蒸气压与温度的关系的图。ln Vp=16.624-5672.8/T,ΔH=47kJ/mol。
要理解的是,本领域技术人员可以在如所附权利要求中表示的本发明的原理和范围内对本文中为解释本发明的性质而描述和例举的细节、材料、步骤和部件布置作出许多额外改变。因此,本发明无意局限于上文给出的实施例和/或附图中的具体实施方案。
Claims (13)
1.在基底上形成含钌层的方法,所述方法包括:
a)提供反应室,该反应室内放置有至少一个基底;
b)向反应室中引入蒸气,所述蒸气包含至少一种具有式[L]mRu(CO)3的化合物,其中L是直链或支链不饱和烃或具有两个或更多个取代基的环状不饱和烃,且m是1或2;和
c)使所述蒸气与基底接触,以使用气相沉积法在基底的至少一个表面上形成含钌层。
2.权利要求1的方法,其中所述气相沉积法是CVD和/或ALD。
3.权利要求1或2的方法,其中所述至少一种化合物选自由Ru(乙烯)2(CO)3、Ru(丙烯)2(CO)3、Ru(丁烯)2(CO)3组成的组。
4.权利要求1或2的方法,其中所述至少一种化合物选自由下述物质组成的组:
Ru(2,4-戊二烯)(CO)3、Ru(2-甲基-2,4-戊二烯)(CO)3、Ru(1,4-戊二烯)(CO)3、Ru(2,4-己二烯)(CO)3、Ru(2,4-己二烯醛)(CO)3、Ru(2,4-庚二烯)(CO)3、Ru(1,4-二甲基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-乙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-正丙基-1,3-环己二烯)(CO)3、Ru(1-甲基-4-异丙基-1,3-环己二烯)(CO)3、Ru(1,5-二甲基-1,4-环己二烯)(CO)3、Ru(1-甲基-5-乙基-1,4-环己二烯)(CO)3、Ru(1-甲基-5-正丙基-1,4-环己二烯)(CO)3和Ru(1-甲基-5-异丙基-1,4-环己二烯)(CO)3。
5.权利要求1或2的方法,其中L是“C=C-C=C”或“C=C-CH2-C=C”。
6.权利要求1或2的方法,其中所述至少一种化合物在大约-20℃至大约100℃、优选大约-20℃至大约30℃、更优选大约-20℃至大约0℃的温度是液体。
7.权利要求2的方法,其中所述气相沉积法是热气相沉积法或等离子体气相沉积法。
8.权利要求1或2的方法,其中所述反应室含有1至200个晶片。
9.权利要求1或2的方法,其中所述气相沉积法在大约0.01Torr(1.33Pa)至大约1000Torr(133,322Pa)、优选大约0.1Torr(13.3Pa)至大约100Torr(13,332.2Pa)的压力范围内进行。
10.权利要求1的方法,其中所述气相沉积法在大约10℃至大约400℃、优选大约25℃至大约350℃、更优选大约50℃至大约300℃的温度范围内进行。
11.权利要求1的方法,进一步包含将反应物引入反应室。
12.权利要求11的方法,其中所述反应物选自由氢(H2)、氨(NH3)、硅烷(SiH4)、二乙基硅烷(SiEt2H2)、它们的受激物类及其混合物组成的组。
13.权利要求11的方法,其中所述反应物选自由氧(O2)、水(H2O)、臭氧(O3)、H2O2、NO、NO2、羧酸(RCOOH)、它们的受激物类及其混合物组成的组。
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-
2010
- 2010-12-30 US US12/981,798 patent/US8357614B2/en active Active
-
2011
- 2011-04-12 CN CN2011800300424A patent/CN102947482A/zh active Pending
- 2011-04-12 KR KR1020127030047A patent/KR20130055608A/ko not_active Application Discontinuation
- 2011-04-12 WO PCT/IB2011/051588 patent/WO2011132116A1/en active Application Filing
- 2011-04-12 SG SG2012077608A patent/SG184939A1/en unknown
- 2011-04-12 EP EP11771667.0A patent/EP2561115A4/en not_active Withdrawn
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110431253A (zh) * | 2017-03-24 | 2019-11-08 | 田中贵金属工业株式会社 | 由铱配合物构成的化学气相沉积用原料及使用该化学气相沉积用原料的化学气相沉积法 |
CN110431253B (zh) * | 2017-03-24 | 2022-02-25 | 田中贵金属工业株式会社 | 由铱配合物构成的化学气相沉积用原料及使用该化学气相沉积用原料的化学气相沉积法 |
CN111655899A (zh) * | 2018-02-12 | 2020-09-11 | 默克专利有限公司 | 使用无氧共反应物气相沉积钌的方法 |
CN113227110A (zh) * | 2019-01-08 | 2021-08-06 | 优美科股份公司及两合公司 | 有机金属化合物 |
CN113227110B (zh) * | 2019-01-08 | 2023-12-05 | 优美科股份公司及两合公司 | 有机金属化合物 |
Also Published As
Publication number | Publication date |
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WO2011132116A1 (en) | 2011-10-27 |
EP2561115A4 (en) | 2013-09-11 |
EP2561115A1 (en) | 2013-02-27 |
US8357614B2 (en) | 2013-01-22 |
US20110256721A1 (en) | 2011-10-20 |
SG184939A1 (en) | 2012-11-29 |
KR20130055608A (ko) | 2013-05-28 |
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