JP7230126B2 - 強誘電体材料としてのケイ素ドープ酸化ハフニウムの堆積のための新規配合物 - Google Patents
強誘電体材料としてのケイ素ドープ酸化ハフニウムの堆積のための新規配合物 Download PDFInfo
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- JP7230126B2 JP7230126B2 JP2021116119A JP2021116119A JP7230126B2 JP 7230126 B2 JP7230126 B2 JP 7230126B2 JP 2021116119 A JP2021116119 A JP 2021116119A JP 2021116119 A JP2021116119 A JP 2021116119A JP 7230126 B2 JP7230126 B2 JP 7230126B2
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- Prior art keywords
- bis
- hafnium
- dimethylamino
- weight
- ethylmethylamino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 93
- 229910000449 hafnium oxide Inorganic materials 0.000 title description 58
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title description 58
- 238000009472 formulation Methods 0.000 title description 53
- 239000000463 material Substances 0.000 title description 33
- 230000008021 deposition Effects 0.000 title description 11
- 239000002243 precursor Substances 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 81
- 125000004122 cyclic group Chemical group 0.000 claims description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 56
- 239000001301 oxygen Substances 0.000 claims description 56
- 229910052760 oxygen Inorganic materials 0.000 claims description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 49
- 229910052710 silicon Inorganic materials 0.000 claims description 49
- 239000010703 silicon Substances 0.000 claims description 48
- 238000000231 atomic layer deposition Methods 0.000 claims description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000010926 purge Methods 0.000 claims description 42
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 37
- -1 alkyl hydrocarbons Chemical class 0.000 claims description 35
- 229910052735 hafnium Inorganic materials 0.000 claims description 35
- QULMGWCCKILBTO-UHFFFAOYSA-N n-[dimethylamino(dimethyl)silyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)N(C)C QULMGWCCKILBTO-UHFFFAOYSA-N 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 31
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 29
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 claims description 25
- IKMXSKDHYPICEK-UHFFFAOYSA-N N[Hf] Chemical compound N[Hf] IKMXSKDHYPICEK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 17
- UYGIYVFPQLCZME-UHFFFAOYSA-N n-[[ethyl(methyl)amino]-dimethylsilyl]-n-methylethanamine Chemical compound CCN(C)[Si](C)(C)N(C)CC UYGIYVFPQLCZME-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 6
- JIGXARPLYFNBCG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C JIGXARPLYFNBCG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 5
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- AHKKZIUZTWZKDR-UHFFFAOYSA-N n-[bis(dimethylamino)-methylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(N(C)C)N(C)C AHKKZIUZTWZKDR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 125000001302 tertiary amino group Chemical group 0.000 claims description 4
- PPPUXCWMGZSIFN-UHFFFAOYSA-N 1-N,1-N',1-N"-triethyl-1-N,1-N',1-N"-trimethyl-2-silylethane-1,1,1-triamine Chemical compound C(C)N(C)C(C[SiH3])(N(CC)C)N(CC)C PPPUXCWMGZSIFN-UHFFFAOYSA-N 0.000 claims description 3
- ITNWBHRKKCGQTA-UHFFFAOYSA-N 2,2,2-tripyrrolidin-1-ylethylsilane Chemical compound N1(CCCC1)C(C[SiH3])(N1CCCC1)N1CCCC1 ITNWBHRKKCGQTA-UHFFFAOYSA-N 0.000 claims description 3
- NIGLKFOWGMYOLU-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1(C=CC=C1)CC NIGLKFOWGMYOLU-UHFFFAOYSA-N 0.000 claims description 3
- OXOIPIBAUDNLEX-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1(C=CC=C1)CC OXOIPIBAUDNLEX-UHFFFAOYSA-N 0.000 claims description 3
- UPGBFWVHZUCRSO-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1(C=CC=C1)CC UPGBFWVHZUCRSO-UHFFFAOYSA-N 0.000 claims description 3
- OVGMXYBODOXHIN-UHFFFAOYSA-N C(C)C[Si](C)(C1=CC=CC=C1)NC Chemical compound C(C)C[Si](C)(C1=CC=CC=C1)NC OVGMXYBODOXHIN-UHFFFAOYSA-N 0.000 claims description 3
- SVXNXAKDMINOTQ-UHFFFAOYSA-N C(C)N(C)[Hf](C1(C=CC=C1)C)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Hf](C1(C=CC=C1)C)(N(CC)C)N(CC)C SVXNXAKDMINOTQ-UHFFFAOYSA-N 0.000 claims description 3
- QSNMTBKFQKBTRF-UHFFFAOYSA-N C(C)N(C)[Hf](C1(C=CC=C1)CC)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Hf](C1(C=CC=C1)CC)(N(CC)C)N(CC)C QSNMTBKFQKBTRF-UHFFFAOYSA-N 0.000 claims description 3
- XFCHQSUHJLEGLK-UHFFFAOYSA-N C(C)N(C)[Si](C1=CC=CC=C1)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Si](C1=CC=CC=C1)(N(CC)C)N(CC)C XFCHQSUHJLEGLK-UHFFFAOYSA-N 0.000 claims description 3
- GSEZYEBZIRQQSP-UHFFFAOYSA-N C(C)N(CC)C(N(CC)CC)(N(CC)CC)[SiH3] Chemical compound C(C)N(CC)C(N(CC)CC)(N(CC)CC)[SiH3] GSEZYEBZIRQQSP-UHFFFAOYSA-N 0.000 claims description 3
- RGJSKIYJBFQSDD-UHFFFAOYSA-N C(C)N(CC)[Hf](C1(C=CC=C1)C)(N(CC)CC)N(CC)CC Chemical compound C(C)N(CC)[Hf](C1(C=CC=C1)C)(N(CC)CC)N(CC)CC RGJSKIYJBFQSDD-UHFFFAOYSA-N 0.000 claims description 3
- QZANQQCQYLHXLS-UHFFFAOYSA-N C(C)N(CC)[Hf](C1(C=CC=C1)CC)(N(CC)CC)N(CC)CC Chemical compound C(C)N(CC)[Hf](C1(C=CC=C1)CC)(N(CC)CC)N(CC)CC QZANQQCQYLHXLS-UHFFFAOYSA-N 0.000 claims description 3
- BNARGUMXHDEANC-UHFFFAOYSA-N C(C)N(CC)[Hf](C1C=CC=C1)(N(CC)CC)N(CC)CC Chemical compound C(C)N(CC)[Hf](C1C=CC=C1)(N(CC)CC)N(CC)CC BNARGUMXHDEANC-UHFFFAOYSA-N 0.000 claims description 3
- YUWUWVULBOJIPN-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1C=CC=C1 YUWUWVULBOJIPN-UHFFFAOYSA-N 0.000 claims description 3
- QRIKEQFIMHWXLK-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1C=CC=C1 QRIKEQFIMHWXLK-UHFFFAOYSA-N 0.000 claims description 3
- ORVYVSSGXIYKDG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1C=CC=C1 ORVYVSSGXIYKDG-UHFFFAOYSA-N 0.000 claims description 3
- MBOMGZHNVNXPDW-UHFFFAOYSA-N CC1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Hf](N(C)C)(N(C)C)C1(C=CC=C1)C MBOMGZHNVNXPDW-UHFFFAOYSA-N 0.000 claims description 3
- WGQUIFUOHSFBNF-UHFFFAOYSA-N CC1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Hf](N(CC)C)(N(C)CC)C1(C=CC=C1)C WGQUIFUOHSFBNF-UHFFFAOYSA-N 0.000 claims description 3
- ZXXWMOMXTOZQFP-UHFFFAOYSA-N CN(C)[Hf](C1(C=CC=C1)C)(N(C)C)N(C)C Chemical compound CN(C)[Hf](C1(C=CC=C1)C)(N(C)C)N(C)C ZXXWMOMXTOZQFP-UHFFFAOYSA-N 0.000 claims description 3
- CXQYVOGCLGBONO-UHFFFAOYSA-N CN(C)[Hf](C1(C=CC=C1)CC)(N(C)C)N(C)C Chemical compound CN(C)[Hf](C1(C=CC=C1)CC)(N(C)C)N(C)C CXQYVOGCLGBONO-UHFFFAOYSA-N 0.000 claims description 3
- LMLOSBGZCSHOFL-UHFFFAOYSA-N CN([Si](O[Si](C)(C)C)(C)C)C Chemical compound CN([Si](O[Si](C)(C)C)(C)C)C LMLOSBGZCSHOFL-UHFFFAOYSA-N 0.000 claims description 3
- USXLKXGKXHGSFF-UHFFFAOYSA-N N,N',N"-triethyl-N,N',N"-trimethyl-1-silylmethanetriamine Chemical compound C(C)N(C)C(N(CC)C)(N(CC)C)[SiH3] USXLKXGKXHGSFF-UHFFFAOYSA-N 0.000 claims description 3
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 3
- VBFLXTQAEDPTLB-UHFFFAOYSA-N N1(CCCC1)[Hf](N1CCCC1)(N1CCCC1)N1CCCC1 Chemical compound N1(CCCC1)[Hf](N1CCCC1)(N1CCCC1)N1CCCC1 VBFLXTQAEDPTLB-UHFFFAOYSA-N 0.000 claims description 3
- UOAMPISOWMWMML-UHFFFAOYSA-N N1(CCCC1)[Si](C)(C)C1=CC=CC=C1 Chemical compound N1(CCCC1)[Si](C)(C)C1=CC=CC=C1 UOAMPISOWMWMML-UHFFFAOYSA-N 0.000 claims description 3
- BAYBTHPPTMXTLT-UHFFFAOYSA-N diethyl(dipyrrolidin-1-yl)silane Chemical compound C1CCCN1[Si](CC)(CC)N1CCCC1 BAYBTHPPTMXTLT-UHFFFAOYSA-N 0.000 claims description 3
- OFKNHDDXWSOGKH-UHFFFAOYSA-N dimethyl(dipyrrolidin-1-yl)silane Chemical compound C1CCCN1[Si](C)(C)N1CCCC1 OFKNHDDXWSOGKH-UHFFFAOYSA-N 0.000 claims description 3
- MRAAXSSHMOFDJR-UHFFFAOYSA-N n-[2-[dimethylamino(dimethyl)silyl]ethyl-dimethylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)CC[Si](C)(C)N(C)C MRAAXSSHMOFDJR-UHFFFAOYSA-N 0.000 claims description 3
- TWGLWJXHSDIEFM-UHFFFAOYSA-N n-[bis(diethylamino)-phenylsilyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](N(CC)CC)(N(CC)CC)C1=CC=CC=C1 TWGLWJXHSDIEFM-UHFFFAOYSA-N 0.000 claims description 3
- IJSFLJAUNGGKJT-UHFFFAOYSA-N n-[bis(dimethylamino)-[2-[tris(dimethylamino)silyl]ethyl]silyl]-n-methylmethanamine Chemical compound CN(C)[Si](N(C)C)(N(C)C)CC[Si](N(C)C)(N(C)C)N(C)C IJSFLJAUNGGKJT-UHFFFAOYSA-N 0.000 claims description 3
- FHBURLBCXNMPJX-UHFFFAOYSA-N n-[bis(dimethylamino)-ethylsilyl]-n-methylmethanamine Chemical compound CC[Si](N(C)C)(N(C)C)N(C)C FHBURLBCXNMPJX-UHFFFAOYSA-N 0.000 claims description 3
- VJDVRUZAQRISHN-UHFFFAOYSA-N n-[bis(dimethylamino)-phenylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](N(C)C)(N(C)C)C1=CC=CC=C1 VJDVRUZAQRISHN-UHFFFAOYSA-N 0.000 claims description 3
- AFKLLDITSFFTER-UHFFFAOYSA-N n-[butyl(diethyl)silyl]methanamine Chemical compound CCCC[Si](CC)(CC)NC AFKLLDITSFFTER-UHFFFAOYSA-N 0.000 claims description 3
- ZRMAZYMYSQYPDU-UHFFFAOYSA-N n-[diethyl-[ethyl(methyl)amino]silyl]-n-methylethanamine Chemical compound CCN(C)[Si](CC)(CC)N(C)CC ZRMAZYMYSQYPDU-UHFFFAOYSA-N 0.000 claims description 3
- JGHGZXZEGQJZPM-UHFFFAOYSA-N n-[diethylamino(diethyl)silyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](CC)(CC)N(CC)CC JGHGZXZEGQJZPM-UHFFFAOYSA-N 0.000 claims description 3
- IOTFVZVUTVVOER-UHFFFAOYSA-N n-[dimethyl(phenyl)silyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](C)(C)C1=CC=CC=C1 IOTFVZVUTVVOER-UHFFFAOYSA-N 0.000 claims description 3
- AVNOVEWSJKFZDN-UHFFFAOYSA-N n-[dimethyl(phenyl)silyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)C1=CC=CC=C1 AVNOVEWSJKFZDN-UHFFFAOYSA-N 0.000 claims description 3
- XFXQXCWQCXPVSY-UHFFFAOYSA-N n-[dimethyl(propyl)silyl]methanamine Chemical compound CCC[Si](C)(C)NC XFXQXCWQCXPVSY-UHFFFAOYSA-N 0.000 claims description 3
- TWQSOHGSGBWNBD-UHFFFAOYSA-N n-[dimethylamino(diethyl)silyl]-n-methylmethanamine Chemical compound CC[Si](CC)(N(C)C)N(C)C TWQSOHGSGBWNBD-UHFFFAOYSA-N 0.000 claims description 3
- WJIJKWCQOIHCCD-UHFFFAOYSA-N n-ethyl-n-triethylsilylethanamine Chemical compound CCN(CC)[Si](CC)(CC)CC WJIJKWCQOIHCCD-UHFFFAOYSA-N 0.000 claims description 3
- ZTAJIYKRQQZJJH-UHFFFAOYSA-N n-methyl-n-triethylsilylmethanamine Chemical compound CC[Si](CC)(CC)N(C)C ZTAJIYKRQQZJJH-UHFFFAOYSA-N 0.000 claims description 3
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- WKSAZWOPSDGBJD-UHFFFAOYSA-N phenyl(tripyrrolidin-1-yl)silane Chemical compound C1CCCN1[Si](C=1C=CC=CC=1)(N1CCCC1)N1CCCC1 WKSAZWOPSDGBJD-UHFFFAOYSA-N 0.000 claims description 3
- ALHOGUGJRCJRQC-UHFFFAOYSA-N triethyl(pyrrolidin-1-yl)silane Chemical compound CC[Si](CC)(CC)N1CCCC1 ALHOGUGJRCJRQC-UHFFFAOYSA-N 0.000 claims description 3
- NQLVIKZJXFGUET-UHFFFAOYSA-N trimethyl(pyrrolidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCC1 NQLVIKZJXFGUET-UHFFFAOYSA-N 0.000 claims description 3
- SSQOSUADOCILEJ-UHFFFAOYSA-N tripyrrolidin-1-ylmethylsilane Chemical compound N1(CCCC1)C(N1CCCC1)(N1CCCC1)[SiH3] SSQOSUADOCILEJ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- TYYSTSWNSKHYFT-UHFFFAOYSA-N C(C)N(C)[Hf](C1C=CC=C1)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Hf](C1C=CC=C1)(N(CC)C)N(CC)C TYYSTSWNSKHYFT-UHFFFAOYSA-N 0.000 claims 1
- IOQGXZXRRNLIDN-UHFFFAOYSA-N CC1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)C1(C=CC=C1)C IOQGXZXRRNLIDN-UHFFFAOYSA-N 0.000 claims 1
- KNTVYNIJAONSRI-UHFFFAOYSA-N [Hf++].C[N-]C.C[N-]C Chemical compound [Hf++].C[N-]C.C[N-]C KNTVYNIJAONSRI-UHFFFAOYSA-N 0.000 claims 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- FFKXFCAPBKXDBS-UHFFFAOYSA-N n-[bis(diethylamino)-ethylsilyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](CC)(N(CC)CC)N(CC)CC FFKXFCAPBKXDBS-UHFFFAOYSA-N 0.000 claims 1
- XIFOKLGEKUNZTI-UHFFFAOYSA-N n-[diethylamino(dimethyl)silyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](C)(C)N(CC)CC XIFOKLGEKUNZTI-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 53
- 239000012071 phase Substances 0.000 description 21
- 150000004820 halides Chemical group 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012686 silicon precursor Substances 0.000 description 5
- 230000032258 transport Effects 0.000 description 5
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- C23C16/401—Oxides containing silicon
-
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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Description
本発明は、電気メモリ用途に関する強誘電体材料としてのケイ素ドープ酸化ハフニウムを堆積させるのに用いることのできる配合物に関する。
本開示に記載されるのは、熱原子層堆積(ALD)又はプラズマ増強原子層堆積(PEALD)プロセス、サイクリック化学気相堆積、プラズマ増強サイクリック化学気相堆積、又はこれらの組み合わせを介してケイ素ドープ酸化ハフニウムを堆積させる新規の配合物又は組成物(これらは交換可能である)、方法及びこれを含む装置である。
本発明は、ヒドロキシル基を有する所与の表面上にケイ素含有フラグメント及びハフニウム含有フラグメントの両方を固定して、0.5~8モル%、好ましくは2~6モル%、最も好ましくは3~5モル%の範囲のケイ素ドーピング量を有するケイ素ドープ酸化ハフニウムを堆積させる有機アミノハフニウム及び有機アミノシラン前駆体化合物の両方を含む配合物又は組成物(配合物及び組成物は交換可能である)を提供することにより従来の前駆体及び方法に関連する問題を解決する。
(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、
(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物と
を含むケイ素ドープ酸化ハフニウム膜を堆積させるための組成物である。R3基を有することにより、ヒドロキシル基に対する有機アミノシラン前駆体の反応性を低下又は増加させることができ、したがって、酸化ハフニウムへの低レベルのケイ素ドーピングのより良好な制御を可能にすると考えられる。
a)反応器に基材を与える工程と、
b)反応器に、(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物とを含む組成物を導入する工程と、
c)反応器をパージガスでパージする工程と、
d)反応器に酸素含有源を導入する工程と、
e)反応器をパージガスでパージする工程と
を含む、基材上にケイ素ドープ酸化ハフニウム膜を堆積させる方法であって、
工程b)からe)が、所望の厚さの膜が堆積されるまで繰り返され、方法が、約100℃~600℃の範囲の温度にて実施される方法である。
反応器中の基材と、
(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物とを含む組成物と
を含み、
100℃~600℃の範囲の温度である、基材上にケイ素ドープ酸化ハフニウム膜を堆積させる装置である。
組成物又は溶媒を含む組成物を用いる容器又はコンテナであって、
組成物が、(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物;及び(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物のうちの少なくとも1種を含む、容器又はコンテナである。
本発明を記載する文脈において(特に以下の特許請求の範囲の文脈において)、「1つの(a)」、「1つの(an)」及び「その(the)」という用語並びに同様の指示語の使用は、本開示で別段の指摘がないか又は文脈によって明確に否定されない限り、単数及び複数の両方を包含すると解されるべきである。
a)反応器に基材を与える工程と、
b)反応器に、(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物とを含む組成物を導入する工程と、
c)反応器をパージガスでパージする工程と、
d)反応器に酸素含有源を導入する工程と、
e)反応器をパージガスでパージする工程と
を含む、基材上に強誘電体材料としてケイ素ドープ酸化ハフニウム膜を堆積させる方法であって、
工程b)からe)が、所望の厚さの膜が堆積されるまで繰り返され、方法が、約100℃~600℃の範囲の温度にて実施される方法が提供される。幾つかの実施態様において、工程d)における酸素含有源は、オゾン、酸素プラズマ等の他の酸素含有源が、シリコン又は窒化金属等の基材材料を潜在的に酸化する可能性があるため、水である。
a)反応器に基材を与える工程と、
b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、x=0、1又は2である。)の式を有する少なくとも1種のハフニウム前駆体化合物を導入する工程と、
c)反応器をパージガスでパージする工程と、
d)反応器に酸素含有源を導入する工程と、
e)反応器をパージガスでパージする工程と、
f)反応器に、(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物とを含む組成物を導入する工程と、
g)反応器をパージガスでパージする工程と、
h)反応器に酸素含有源を導入する工程と、
i)反応器をパージガスでパージする工程と
を含む、基材上にケイ素ドープ酸化ハフニウム膜を堆積させる方法であって、
工程b)からe)が、所望の厚さの膜が堆積されるまで繰り返され、方法が、約100℃~600℃の範囲の温度にて実施される方法が提供される。オゾン、酸素プラズマ等の他の酸素含有源が、シリコン又は窒化金属等の基材材料を潜在的に酸化する可能性があるため、幾つかの実施態様において、工程d)における酸素含有源は水であり、他の実施態様において、工程d)及びh)における酸素含有源は両方とも水である。
反応器中の基材と、
(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物とを含む組成物と
を含み、
100℃~600℃の範囲の温度である、基材上にケイ素ドープ酸化ハフニウム膜を堆積させる装置が提供される。
少なくとも1種の前駆体化合物、又は溶媒を含む少なくとも1種の前駆体化合物を用いる容器又はコンテナであって、
少なくとも1種の前駆体化合物が、(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物;及び(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物からなる群から選択される、容器又はコンテナである。
(1)(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物;及び(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物、並びに
(2)(a)RxR3Si(NR1R2)3-x(式中、Rはハライド(Cl、Br、I)、又は直鎖若しくは分岐鎖C1~C6アルキルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、R3は直鎖又は分岐鎖C1~C6アルキルからなる群から選択され、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノシラン前駆体化合物;(b)LxHf(NR1R2)4-x(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルから選択され、R1及びR2は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、x=0、1又は2である。)の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物;及び(c)溶媒
からなる群から選択される。
以下の例において、別段の記載がない限り、特性は、基材として5~20Ωcmの抵抗率のシリコンウェハ上に堆積されたサンプル膜から得られ、またはPVD TiNウェハは、基材としてTiN500Å/Ti50Å/熱SiO2 3000Å/Siサブ構造を有する。全ての膜堆積は、13.56MHz直接プラズマのシャワーヘッドデザインを有するCN-1反応器を用いて実施される。典型的なプロセス条件において、別段の記載がない限り、チャンバ圧力は、約1~約5Torrの範囲の圧力にて固定される。追加の不活性ガスを用いてチャンバ圧力が維持される。
シリコンウェハを13.56MHz直接プラズマのシャワーヘッドデザインを備えるCN‐1反応器に入れ、1tоrrのチャンバ圧力で、200℃、又は250℃、又は300℃に加熱した。
a.反応器へ配合物前駆体を導入する
アルゴンフロー:1000sccm
配合物前駆体パルス:1~5秒
b.不活性ガスパージ
アルゴンフロー:1000sccm
パージ時間:20秒
c.オゾンを導入する
アルゴンフロー:1000sccm
オゾンパルス:5~20秒
d.パージ
アルゴンフロー:1000sccm
パージ時間:20秒
シリコンウェハを13.56MHz直接プラズマのシャワーヘッドデザインを備えるCN‐1反応器に入れ、1tоrrのチャンバ圧力で300℃に加熱する。
a.反応器へ配合物前駆体を導入する
アルゴンフロー:1000sccm
配合物前駆体パルス:1~5秒
b.不活性ガスパージ
アルゴンフロー:1000sccm
パージ時間:20秒
c.水蒸気を導入する
アルゴンフロー:1000sccm
水パルス:1~10秒
d.パージ
アルゴンフロー:1000sccm
パージ時間:20秒
シリコンウェハを13.56MHz直接プラズマのシャワーヘッドデザインを備えるCN‐1反応器に入れ、1tоrrのチャンバ圧力で300℃に加熱する。
a.反応器へ配合物前駆体を導入する
アルゴンフロー:1000sccm
配合物前駆体パルス:1~5秒
b.不活性ガスパージ
アルゴンフロー:1000sccm
パージ時間:20秒
c.酸素プラズマを導入する
アルゴンフロー:1000sccm
酸素プラズマパルス:2~10秒
d.パージ
アルゴンフロー:1000sccm
パージ時間:20秒
ビス(ジメチルアミノ)ジメチルシランとテトラキス(ジメチルアミノ)ハフニウム(TDMAH)の混合割合を変更することにより、幾つかの配合物を作った。
テトラキス(ジメチルアミノ)ハフニウム(TDMAH)中に約9質量%のビス(ジメチルアミノ)ジメチルシランを含む配合物の約1gを、窒素下、密閉されたステンレス鋼チューブ内で60℃にて7日間加熱した。
テトラキス(ジメチルアミノ)ハフニウムに種々の量のビス(ジメチルアミノ)メチルシランを加えることにより、幾つかの配合物を作った。これらの混合物の液相が1H及び13C NMR分光法により分析された際、ビス(ジメチルアミノ)メチルシラン及びテトラキス(ジメチルアミノ)ハフニウムが、多量のトリス(ジメチルアミノ)メチルシラン、及びジメチルアミノハフニウムヒドリド種と一致する幾つかの他の不純物と共に主成分として同定された。これは、1つのSi-H基を有するビス(ジメチルアミノ)メチルシラン及びテトラキス(ジメチルアミノ)ハフニウム間でアミノ/ヒドリド交換が起こったことを示し、それらが本発明の目的のために互いに適合しないことを示す。
Claims (9)
- 基材上にケイ素、ハフニウム、及び酸素を含む膜を堆積させる方法であって、
a)反応器に基材を与える工程と、
b)前記反応器に、
(i)RxR3Si(NR1R2)3-x
(式中、Rは、直鎖若しくは分岐鎖C1~C6アルキルであり、
R1、R2及びR3は独立して直鎖又は分岐鎖C1~C6アルキルから選択され、
有機アミノ基におけるR1及びR2は結合して環状環構造を形成するか、環状環構造を形成するように結合せず、
x=0、1又は2である。)
の式を有する少なくとも1種の有機アミノシラン前駆体化合物と、
(ii)LxHf(NR1R2)4-x
(式中、Lはシクロペンタジエニル、又はアルキル置換シクロペンタジエニルであり、
R1及びR2は独立して有機アミノ基における直鎖又は分岐鎖C1~C6アルキルから選択され、
R1及びR2は結合して環状環構造を形成するか、R1及びR2は環状環構造を形成するように結合せず、
x=0、1又は2である。)
の式を有する少なくとも1種の有機アミノハフニウム前駆体化合物と
を含む組成物を導入する工程と、
c)前記反応器をパージガスでパージする工程と、
d)前記反応器に酸素含有源を導入する工程と、
e)前記反応器をパージガスでパージする工程と
を含み、
前記組成物の融点が≦30℃であり、
前記少なくとも1種の有機アミノシラン前駆体化合物と、前記少なくとも1種の有機アミノハフニウム前駆体化合物が、同じ有機アミノ基を有しており、
前記酸素含有源が、酸素プラズマ、オゾン、水蒸気、水蒸気プラズマ、酸化窒素プラズマ、酸化炭素プラズマ、及びこれらの組み合わせからなる群から選択され、
前記パージガスが、アルゴン(Ar)、窒素(N2)、ヘリウム(He)、ネオン、水素(H2)、及びこれらの組み合わせからなる群から選択され、
堆積プロセスが、熱原子層堆積(ALD)、プラズマ増強原子層堆積(PEALD)プロセスおよびそれらの組み合わせからなる群から選択され、
前記方法が、100℃~600℃の範囲の温度にて実施され、b)からe)が、所望の厚さの膜が堆積されるまで繰り返される方法。 - 前記組成物が、直接液体注入により輸送される、請求項1に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体化合物が、トリス(ジメチルアミノ)メチルシラン、トリス(ジエチルアミノ)メチルシラン、トリス(エチルメチルアミノ)メチルシラン、トリス(ピロリジノ)メチルシラン、トリス(ジメチルアミノ)エチルシラン、トリス(ジエチルアミノ)エチルシラン、トリス(エチルメチルアミノ)エチルシラン、トリス(ピロリジノ)エチルシラン、ビス(ジメチルアミノ)ジメチルシラン、ビス(ジエチルアミノ)ジメチルシラン、ビス(エチルメチルアミノ)ジメチルシラン、ビス(ピロリジノ)ジメチルシラン、ビス(ジメチルアミノ)ジエチルシラン、ビス(ジエチルアミノ)ジエチルシラン、ビス(エチルメチルアミノ)ジエチルシラン、ビス(ピロリジノ)ジエチルシラン、ジメチルアミノトリメチルシラン、ジエチルアミノトリメチルシラン、エチルメチルアミノトリメチルシラン、ピロリジノトリメチルシラン、ジメチルアミノトリエチルシラン、ジエチルアミノトリエチルシラン、エチルメチルアミノトリエチルシラン、ピロリジノトリエチルシラン、ジメチルアミノフェニルジメチルシラン、ジエチルアミノフェニルジメチルシラン、エチルメチルアミノフェニルジメチルシラン、ピロリジノフェニルジメチルシラン、トリス(ジメチルアミノ)フェニルシラン、トリス(ジエチルアミノ)フェニルシラン、トリス(エチルメチルアミノ)フェニルシラン、トリス(ピロリジノ)フェニルシラン、1-ジメチルアミノ-1,1,3,3,3-ペンタメチルジシロキサン、1,1,1,4,4,4-ヘキサキス(ジメチルアミノ)-1,4-ジシラブタン、2,5-ビス(ジメチルアミノ)-2,5-ジメチル-2,5-ジシラヘキサン及びこれらの組み合わせからなる群から選択され、
前記少なくとも1種の有機アミノハフニウム前駆体化合物が、テトラキス(ジメチルアミノ)ハフニウム(TDMAH)、テトラキス(ジエチルアミノ)ハフニウム(TDEAH)、テトラキス(エチルメチルアミノ)ハフニウム(TEMAH)、テトラキス(ピロリジノ)ハフニウム、シクロペンタジエニルトリス(ジメチルアミノ)ハフニウム(CpHf(NMe2)3)、メチルシクロペンタジエニルトリス(ジメチルアミノ)ハフニウム(MeCpHf(NMe2)3)、エチルシクロペンタジエニルトリス(ジメチルアミノ)ハフニウム(EtCpHf(NMe2)3)、シクロペンタジエニルトリス(エチルメチルアミノ)ハフニウム(CpHf(NMeEt)3)、メチルシクロペンタジエニルトリス(エチルメチルアミノ)ハフニウム(MeCpHf(NMeEt)3)、エチルシクロペンタジエニルトリス(エチルメチルアミノ)ハフニウム(EtCpHf(NMeEt)3)、シクロペンタジエニルトリス(ジエチルアミノ)ハフニウム(CpHf(NEt2)3)、メチルシクロペンタジエニルトリス(ジエチルアミノ)ハフニウム(MeCpHf(NEt2)3)、エチルシクロペンタジエニルトリス(ジエチルアミノ)ハフニウム(EtCpHf(NEt2)3)、ビス(シクロペンタジエニル)ビス(ジメチルアミノ)ハフニウム(Cp2Hf(NMe2)2)、ビス(メチルシクロペンタジエニル)ビス(ジメチルアミノ)ハフニウム((MeCp)2Hf(NMe2)2)、ビス(エチルシクロペンタジエニル)ビス(ジメチルアミノ)ハフニウム((EtCp)2Hf(NMe2)2)、ビス(シクロペンタジエニル)ビス(エチルメチルアミノ)ハフニウム(Cp2Hf(NMeEt)2)、ビス(メチルシクロペンタジエニル)ビス(エチルメチルアミノ)ハフニウム((MeCp)2Hf(NMeEt)2)、ビス(エチルシクロペンタジエニル)ビス(エチルメチルアミノ)ハフニウム((EtCp)2Hf(NMeEt)2)、ビス(シクロペンタジエニル)ビス(ジエチルアミノ)ハフニウム(Cp2Hf(NEt2)2)、ビス(メチルシクロペンタジエニル)ビス(ジエチルアミノ)ハフニウム((MeCp)2Hf(NEt2)3)、ビス(エチルシクロペンタジエニル)ビス(ジエチルアミノ)ハフニウム((EtCp)2Hf(NEt2)2)、(N-メチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(ジメチルアミノ)ハフニウム、(N-エチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(ジメチルアミノ)ハフニウム、(N-メチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(ジエチルアミノ)ハフニウム、(N-エチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(ジエチルアミノ)ハフニウム、(N-メチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(エチルメチルアミノ)ハフニウム、(N-エチル-2,4-シクロペンタジエン-1-エタンアミノ)ビス(エチルメチルアミノ)ハフニウム、及びこれらの組み合わせからなる群から選択される、請求項1に記載の方法。 - 前記組成物が、ビス(ジメチルアミノ)ジメチルシラン及びテトラキス(ジメチルアミノ)ハフニウムを含む、請求項1に記載の方法。
- 前記組成物が、エーテル、第三級アミン、アルキル炭化水素、芳香族炭化水素、シロキサン、第三級アミノエーテル、及びこれらの組み合わせからなる群から選択される(iii)溶媒をさらに含む、請求項1に記載の方法。
- 前記組成物が、反応器に直接液体注入により輸送される、請求項1に記載の方法。
- 前記酸素含有源が、アルゴン、ヘリウム、窒素、水素、及びこれらの組み合わせからなる群から選択される不活性ガスをさらに含む、請求項1に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体化合物が、0.10~99.90質量%、0.10~30.00質量%、0.10~20.00質量%、0.10~10.00質量%、5.00~30.00質量%、5.00~20.00質量%、5.00~10.00質量%、及び0.10~5.00質量%からなる群から選択される範囲を有し、
前記少なくとも1種の有機アミノハフニウム前駆体化合物が、0.10~99.00質量%、0.10~30.00質量%、0.10~20.00質量%、0.10~10.00質量%、5.00~30.00質量%、5.00~20.00質量%、5.00~10.00質量%、及び0.10~5.00質量%からなる群から選択される範囲を有する、請求項1に記載の方法。 - エーテル、第三級アミン、アルキル炭化水素、芳香族炭化水素、シロキサン、第三級アミノエーテル、及びこれらの組み合わせからなる群から選択される(iii)溶媒をさらに含み、
前記少なくとも1種の有機アミノシラン前駆体化合物が、0.10~99.90質量%、10.00~90.00質量%、20.00~80.00質量%、30.00~70.00質量%、及び40.00~60.00質量%からなる群から選択される範囲を有し、
前記少なくとも1種の有機アミノハフニウム前駆体化合物が、0.10~99.00質量%、10.00~90.00質量%、20.00~80.00質量%、30.00~70.00質量%、及び40.00~60.00質量%からなる群から選択される範囲を有する、請求項1に記載の方法。
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KR102363103B1 (ko) | 2022-02-16 |
US11081337B2 (en) | 2021-08-03 |
JP6916297B2 (ja) | 2021-08-11 |
US20180269057A1 (en) | 2018-09-20 |
JP2021180320A (ja) | 2021-11-18 |
KR20190120431A (ko) | 2019-10-23 |
EP3596249A1 (en) | 2020-01-22 |
EP3596249A4 (en) | 2020-12-02 |
SG11201908485TA (en) | 2019-10-30 |
CN110573651A (zh) | 2019-12-13 |
CN110573651B (zh) | 2022-07-22 |
TW201835373A (zh) | 2018-10-01 |
WO2018170126A1 (en) | 2018-09-20 |
TWI734896B (zh) | 2021-08-01 |
JP2020511797A (ja) | 2020-04-16 |
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