CN101187012A - 催化剂辅助的高k材料的硅酸盐的沉积方法 - Google Patents
催化剂辅助的高k材料的硅酸盐的沉积方法 Download PDFInfo
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 62
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 35
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title abstract 5
- 238000000151 deposition Methods 0.000 title description 23
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 239000012686 silicon precursor Substances 0.000 claims abstract description 43
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 160
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910021529 ammonia Inorganic materials 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 238000007654 immersion Methods 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 8
- 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 4
- 239000000376 reactant Substances 0.000 abstract description 12
- 238000002791 soaking Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 238000000231 atomic layer deposition Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 24
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 238000012545 processing Methods 0.000 description 11
- CCRXBARNRYTTFW-UHFFFAOYSA-N [Hf].[Si](O)(O)(O)O Chemical compound [Hf].[Si](O)(O)(O)O CCRXBARNRYTTFW-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- -1 halogenide Chemical class 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- AHJCYBLQMDWLOC-UHFFFAOYSA-N n-methyl-n-silylmethanamine Chemical compound CN(C)[SiH3] AHJCYBLQMDWLOC-UHFFFAOYSA-N 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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- 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]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
- C23C16/45546—Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
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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
- C23C16/22—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
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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
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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
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- 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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- 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
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Abstract
本发明公开一种高-k硅酸盐原子层沉积方法。为了产生硅酸铪层,衬底可暴露于铪前驱物、氧化剂脉冲、硅前驱物脉冲和其它氧化剂脉冲。催化剂可额外地与一种或多种反应物穿过分离的入口流入腔室中。选择性地,催化剂可在反应物引入到浸泡程序之前流入到腔室。通过穿过分离的入口协流催化剂或者通过执行催化剂浸泡,硅酸铪形成可在快速和/或在低温下执行。
Description
技术领域
本发明主要涉及一种通过原子层沉积(ALD)在衬底上沉积硅酸铪层的方法。
背景技术
在半导体处理领域、平板显示器处理或其它电子器件处理中,气相沉积工艺在将材料沉积到衬底上起重要作用。随着电子器件的几何尺寸持续缩减而器件密度持续增加,部件的尺寸和深宽比变得越来越有挑战性。因此,材料共形沉积以形成这些器件变得越来越重要。
虽然已经证明传统的化学气相沉积(CVD)可成功用于下降到约0.15μm的器件几何尺寸和深宽比,但是更有挑战性的器件几何尺寸需要可选的沉积技术。引起相当大关注的一种技术是ALD。在ALD工艺期间,反应气体顺序引入到包含衬底的工艺腔室中。一般地,第一反应物脉冲到工艺腔室中且被吸附在衬底表面上。然后,第二反应物被脉冲到工艺腔室中并与第一反应物反应以形成沉积材料。抽吸和/或净化步骤可在每种反应物气体的输送期间实施。净化步骤可由载气连续净化或在反应物气体的输送之间脉冲净化。
通过ALD形成硅酸铪是本领域中公知的工艺。在通过ALD形成硅酸铪中,铪前驱物可脉冲到伴有氧化源的腔室中。之后,硅前驱物脉冲到伴有氧气源的腔室中。当沉积高-k硅酸盐时,氧化源存在许多挑战,原因在于氧化源与催化剂的反应。
因此,在该领域中需要一种在ALD中沉积催化剂辅助的高-k材料的硅酸盐的方法。
发明内容
本发明公开一种硅酸铪ALD方法以作为高-k硅方法的示例。为了产生硅酸铪层,衬底可暴露于铪前驱物脉冲、氧化剂脉冲、硅前驱物脉冲和其它氧化剂脉冲。催化剂可额外地与一种或多种反应物穿过分离的入口同向流入腔室中。选择性地,催化剂可在反应物引入到浸泡程序之前流入到腔室。通过穿过分离的入口协流催化剂或者通过执行催化剂浸泡,硅酸铪形成可在快速和/或在低温下执行。
在一个实施方式中,公开一种硅酸铪沉积方法。该方法包含顺序地将衬底放置在腔室中,将该衬底暴露于铪前驱物,将该衬底暴露于第一催化剂浸泡,将该衬底暴露于第一氧化源,将该衬底暴露于硅前驱物,将该衬底暴露于第二催化剂浸泡,以及然后将该衬底暴露于第二氧化源。
在其它实施方式中,公开一种硅酸铪沉积方法。该方法包含顺序地将衬底放置在腔室中;将该衬底暴露于铪前驱物;将该衬底暴露于第一氧化源以及第一硅化剂,其中该第一催化剂和第一氧化源穿过分离的入口流入腔室中;将该衬底暴露于硅前驱物;以及然后将该衬底暴露于第二氧化源和第二催化剂,其中该第二催化剂和第二氧化源穿过分离的入口流入腔室中。
在又一实施方式中,公开一种硅酸铪沉积方法。该方法包含顺序地将衬底放置在腔室中;将该衬底暴露于铪前驱物;将该衬底暴露于水和吡啶,其中所述水和吡啶穿过分离的入口流入腔室中;将该衬底暴露于六氯乙硅烷,以及然后将该衬底暴露于水和吡啶,其中该水和吡啶穿过分离的入口流入腔室中。
附图简要说明
为了能详细理解本发明的以上所述特征,将参照实施方式对以上的概述进行更加详细的描述,其中部分实施方式在附图中示出。然而,应该理解,附图仅示出了本发明的典型实施方式,因此不应理解为本发明范围的限定,因为本发明还承认其它等效实施方式。
图1A是根据本发明的一个实施方式的装置100的示意性视图;
图1B是根据本发明的一个实施方式的注射器的示意性视图;
图2是根据本发明的一个实施方式的沉积方法的流程图200;
图3是根据本发明的另一实施方式的沉积方法的流程图300;
图4是根据本发明又一实施方式的沉积方法的流程图400;
图5是根据本发明的再一实施方式的沉积方法的流程图500;
为了便于理解,尽可能使用相同的附图标记表示图中共有的相同元件。预期在一个实施方式中公开的元件可以有利地用于其它实施方式而不用特殊叙述。
具体实施方式
描述硅酸铪ALD方法为高-k硅方法的示例。为了产生硅酸铪层,衬底可暴露于铪前驱物的脉冲、氧化剂的脉冲、硅前驱物的脉冲和其它氧化剂的脉冲。硅化剂可额外地穿过分离的入口与一种或多种反应物协流到腔室中。可选地,硅化剂可在反应物引入到浸泡工序之前流入到腔室。通过穿过分离的入口与催化剂协流或者通过执行催化剂浸泡,硅酸铪形成工艺可以快速和/或在低温下执行。
图1A是根据本发明的一个实施方式的装置100的示意性视图。装置100包含真空腔室102。装置100可为包含其上放置衬底104的一个或多个基座106的批处理装置100。在一个实施方式中,装置100可为单一的衬底104装置。在另一实施方式中,可使用晶圆舟,其可容纳一个或多个衬底而不用基座。其有利于同时处理多个衬底104,从而增加产量。批处理的一个问题在于保持晶圆到晶圆的均匀性。
前驱物可穿过注射送气室108送入到装置100。注射送气室108可包含一起围绕并限定注射送气腔122的气室壁110和注射板114。注射板114具有多个孔116,前驱气体、净化气体和载气穿过该多个孔可流入120到真空腔室102。注射板114将注射送气室108与真空腔室102分离,使得真空腔室102是注射送气室108的低压侧部112。前驱气体、净化气体和载气可穿过导管118a-118d引入到注射送气室108。
装置100可穿过排气增压室124排气。排气增压室可包含围绕并限定排气增压室128的排气板126和气室壁130。多个孔132可存在于排气板126中。气体可穿过排气口136从排气增压室124排出。
额外的气体可穿过导管134引入到排气增压室124。额外的气体可除去或转化反应副产物,否则其将凝聚在排气增压室124和真空腔室102的表面上。节流阀138可控制真空腔室102的压力。
当通过ALD形成高-k硅酸盐时,可将高-k前驱物,诸如铪前驱物输送至装置100。可用于沉积硅酸铪层的示例性铪前驱物包括包含配体的化合物诸如卤化物、烷氨基、环戊二烯基、烷基、醇化物及其派生物或组合。用于铪前驱物的硅酸铪化合物可包括HfCl4、HfI4和HfBr。用作铪前驱物的铪氨基化合物包括(RR’N)4Hf,其中R或R’为独立的氢、甲基、乙基、丙基或丁基。用于沉积含铪材料的铪前驱物包括(Et2N)4Hf(TDEAH)、(Me2N)4Hf(TDMAH)、(MeEtN)4Hf(TEMAH)、(tBuC5H4)2HfCl2、(C5H5)2HfCl2、(EtC5H4)2HfCl2、(Me5C5)2HfCl2、(Me5C5)HfCl3、(iPrC5H4)2HfCl2 (iPrC5H4)HfCl3、(tBuC5H4)2HfMe2、(acac)4Hf、(hfac)4Hf、(tfac)4Hf、(thd)4Hf、(NO3)4Hf、(tBuO)4Hf、(iPrO)4Hf、(EtO)4Hf、(MeO)4Hf或其派生物。
应该理解虽然本发明已经在以上关于硅酸铪进行描述,但是本发明还可应用于其它高-k材料诸如含Al、Zr、La和Sr的硅酸盐。可使用的高-k前驱物的实施例可在美国专利申请No.2006/0019033 A1中找出,在此引入其全部内容作为参考。
也可将硅前驱物也可输送到装置100。用于沉积硅酸铪的示例性硅前驱物包括硅烷、烷基硅烷、氨基硅烷、烷氨基硅烷、硅烷醇或烷氧基硅烷。例如,硅前驱物可包括(Me2N)4Si,(Me2N)3SiH,(Me2N)2SiH2,(Me2N)SiH3,(Et2N)4Si,(Et2N)3SiH,(MeEtN)4Si,(MeEtN)3SiH,Si(NCO)4,MeSi(NCO)3,SiH4,Si2H6,SiCl4,Si2Cl6,MeSiCl3,HSiCl3,Me2SiCl2,H2SiCl2,MeSi(OH)3,Me2Si(OH)2,(MeO)4Si,(EtO)4Si或其派生物。其它用作硅前驱物的烷氨基硅烷化合物包括(RR’N)4SiHn,其中R或R’为独立的氢、甲基、乙基、丙基或丁基。并且n=0~3。其它烷氧基硅烷可通过一般化学式(RO)4-NSiLn描述,其中R=甲基、乙基、丙基或丁基且L=H、OH、F、Cl、Br或I及其混合物。另外,较高的烷基可用作本发明部分实施方式中的硅前驱物。较高的烷基在共同转让的美国专利申请No.US 2004/0224089 A1中公开,在此引入其全部内容作为参考。在部分实施方式中,硅前驱物可包括三(二甲基氨基)硅烷((Me2N)3SiH或三-DMAS)、四(二甲基氨基)硅烷((Me2N)4Si或TDMAS)或其它二烷基氨基硅烷,而在其它实施方式中硅前驱物可包含硅烷(SiH4)或硅烷醇。在又一实施方式中,硅前驱物可包含六氯乙硅烷(HCDS)。在再一实施方式中,硅前驱物可包含四-乙氧基-硅烷(TEOS)。
用于在ALD工艺中形成硅酸铪的氧化源可包含氧气(O2)、臭氧(O3)、原子氧(O)、过氧化氢(H2O2)、一氧化二氮(N2O)、一氧化氮(NO)、五氧化二氮(N2O5)、二氧化氮(NO2)、水(H2O)、乙醇及其派生物或组合。在示例性实施方式中,氧化源包含水(H2O)。
当使用水作为氧化源时,供应催化剂以允许ALD与在不存在催化剂情形下发生相比在较快速度和较低温度下进行。可使用的催化剂的实施例包括氨和吡啶。吡啶和水相互作用。因此,当水和吡啶一起穿过相同的进入导管协流到腔室时,水和吡啶可在到达腔室之前互相作用。当水和吡啶相互作用时,吡啶不再有效地用作催化剂,因此不增加ALD沉积速度。
为了避免水和吡啶在达到腔室之前互相作用,吡啶和水可使用分离的输送导管分离注射送气室而协流到腔室。图1B是根据本发明的一个实施方式的注射送气室108a-c的示意性视图。如在图1B中所示,每个导管118a-118d送入到分离的注射送气室108a-108d。因此,可防止吡啶-水的相互作用直到吡啶和水达到腔室。
硅前驱物诸如HCDS和TEOS与铪前驱物诸如TDMAH、TEMAH、TDEAH和HfCl4不与吡啶相互作用。因此,硅前驱物和吡啶可使用相同的导管和注射送气室协流到腔室。在一个实施方式中,吡啶和硅前驱物可使用相同的导管和注射送气室流到腔室。在另一实施方式中,吡啶和硅前驱物可使用分离的导管和注射送气室流到腔室。另外,铪前驱物和吡啶可使用相同的导管和注射送气室协流到腔室。在一个实施方式中,吡啶和铪前驱物可使用相同的导管和注射送气室流到腔室。另一实施方式中,吡啶和铪前驱物可使用分离的导管和注射送气室流到腔室。
使用分离注射送气室和导管协流吡啶和水的可选实施例为在将水引入到腔室之前将衬底暴露于吡啶浸泡剂。吡啶浸泡可包含将衬底暴露于吡啶而不用引入其它前驱物或氧化剂诸如水。衬底可暴露于吡啶足以用吡啶使衬底饱和的时间。在一个实施方式中,吡啶浸泡进行大于约10秒的时间。通过执行吡啶浸泡,足够的催化剂可存在于腔室内和衬底表面,以确保当引入水前驱物时存在催化剂。由于吡啶已经在腔室中,所以所有的吡啶不会通过在到达腔室之前与水相互作用而消耗。当执行吡啶浸泡时,额外的吡啶可根据需要与氧化剂协流,与硅前驱物协流,以及与铪前驱物协流。在一个实施方式中,当硅前驱物和随后的水输送到腔室时,执行吡啶浸泡并且嘧啶持续流到腔室中。在另一实施方式中,执行吡啶浸泡并且在水输送和硅前驱物输送期间停止吡啶输送。在又一实施方式中,当铪前驱物以及随后水输送到腔室时,吡啶浸泡执行并且嘧啶持续流到腔室中。在再一实施方式中,在水输送和铪前驱物输送期间,执行吡啶浸泡并停止吡啶输送。吡啶允许在低温诸如从约100摄氏度到约300摄氏度下发生反应。在一个实施方式中,温度范围为约150摄氏度到约200摄氏度。随着温度降低,硅酸铪的生长速度增加。
当使用氨作为催化剂时,用与以上关于吡啶浸泡相似的方式执行氨浸泡。氨可与铪和硅前驱物使用相同或分离的入口协流到腔室。当前驱物流到腔室时,还可停止氨流。当将氧化源提供到腔室时,可额外地将氨提供到腔室。可使用相同的入口或使用与氧化源分离的入口提供氨。另外,在引入氧化源之前,氨浸泡可存在或不存在。
图2是根据本发明的一个实施方式的沉积方法的流程图200。首先,一个或多个衬底可放置到工艺腔室中(步骤202)。然后,衬底可可选地暴露于吡啶浸泡。吡啶浸泡发生至少10秒。在可选的吡啶浸泡之后,铪前驱物的脉冲引入到腔室(步骤204)。当铪前驱物引入到腔室时,可选地将吡啶提供到腔室。
在铪前驱物脉冲之后,可净化和/或抽吸腔室(步骤206)。可使用的示例性净化气体包括诸如氩的惰性气体。在一个实施方式中,净化气体可包含氮气。可抽吸腔室以去除净化气体和可能存在于腔室中的任何残留铪前驱物。在一个实施方式中,不执行抽吸步骤,从而仅执行净化步骤。可选地,可去除净化步骤,从而抽吸腔室以去除铪前驱物。在一个实施方式中,抽吸可发生在净化气体引入之前和之后。在另一实施方式中,净化和抽吸步骤都可重复。抽吸和/或净化可发生多次。在又一实施方式中,净化和抽吸可结合为一个步骤。
在抽吸和/或净化之后,可发生吡啶浸泡(步骤208)。在第一吡啶浸泡之后,氧源诸如水的脉冲可引入到腔室(步骤210)。当氧源引入到腔室时,吡啶可以可选地协流到腔室中。如果吡啶与水协流到腔室中,则吡啶和水将具有到腔室中的分离入口,以便水和吡啶不通过相同的导管和入口同时流入腔室。
在将氧源脉冲提供到腔室之后,可如上所述抽吸和/或净化腔室(步骤212)。在抽吸和/或净化之后,可选地进行其它吡啶浸泡。之后,硅前驱物可脉冲到腔室中(步骤214)。当硅前驱物引入到腔室中时,吡啶可选地提供到腔室中。在硅前驱物脉冲之后,可再次抽吸和/净化腔室(步骤216)。
在抽吸和/或净化之后,衬底可暴露于其它吡啶浸泡(步骤218)。吡啶浸泡可在以上所述的存在吡啶浸泡的相同处理条件下发生。在吡啶浸泡之后,氧化源诸如H2O的脉冲可引入到腔室(步骤220)。由于吡啶还从浸泡步骤存在于腔室内,所以存在足够的吡啶用作催化剂。在将衬底暴露于氧化源诸如H2O之后,可在如以上所述条件下执行其它抽吸和/或净化循环(步骤222)。
在抽吸和/或净化腔室之后,可测量硅酸铪层的厚度以确定是否已经达到预定的硅酸铪厚度(步骤224)。如果还没有达到预定厚度,则可重复沉积工序。如果已经达到了预定厚度,则工艺终止(步骤226)。
图3是根据本发明的另一实施方式的沉积方法的流程图300。首先,将个一个或多个衬底放置在工艺腔室中(步骤302)。然后衬底可选地暴露于氨浸泡。氨浸泡发生至少10秒。在可选的氨浸泡之后,可将铪前驱物的脉冲引入到腔室(步骤304)。当铪前驱物引入到腔室时,可选地将氨提供到腔室。
在铪前驱物的脉冲之后,可如上所述净化和/或抽吸腔室(步骤306)。在抽吸和/或净化之后,可发生氨浸泡(步骤308)。在氨浸泡之后,氧源诸如水的脉冲可引入到腔室(步骤310)。当氧源引入到腔室时,氨可选地协流到腔室中。可穿过相同的导管或穿过分离的导管将氨和氧源诸如水提供到腔室。
在已经将氧源脉冲提供到腔室之后,可如上所述在此抽吸和/或净化腔室(步骤312)。在抽吸和/或净化之后,可选地发生其它氨浸泡。之后,硅前驱物可脉冲至腔室中(步骤314)。当硅前驱物引入到腔室中时,可选地将氨提供到腔室。在硅前驱物脉冲之后,可再次抽吸和/或净化腔室(并步骤316)。
在抽吸和/或净化之后,衬底可暴露于其它氨浸泡(步骤318)。氨浸泡可在对于以上所述的氨浸泡相同的处理条件下发生。在氨浸泡之后,氧源诸如H2O脉冲可引入到腔室(步骤320)。在衬底暴露于氧源诸如H2O之后,可在如以上所述的条件下执行其它抽吸和/或净化循环(步骤322)。
在已经抽吸和/或净化腔室之后,可测量硅酸铪的厚度以确定是否已经达到预定的硅酸铪厚度(步骤324)。如果还没有达到预定厚度,则重复沉积工序。如果已经达到了预定厚度,则工艺终止(步骤326)。
图4是根据本发明的又一实施方式的沉积方法的流程图400。首先,将一个或多个衬底放置在工艺腔室中(步骤402)。可将铪前驱物的脉冲引入到腔室(步骤404)。吡啶可选地与铪前驱物以以上所述的相似方式协流到腔室。在铪前驱物脉冲之后,可如上所述净化和/或抽吸腔室(步骤406)。
在抽吸和/或净化之后,将氧源诸如水的脉冲引入到腔室(步骤408)。在将氧源引入到腔室时,吡啶可协流到腔室中。吡啶和水将以分离的入口流入腔室,从而水和吡啶不通过相同的导管和入口同时流入腔室。
在已经将氧源和吡啶脉冲提供到腔室之后,可如上所述在此抽吸和/或净化腔室(步骤410)。之后,硅前驱物可脉冲到腔室中(步骤412)。吡啶可选地与硅前驱物用以上所述的相似方式协流到腔室。在硅前驱物脉冲之后,可在此抽吸和/或净化腔室(步骤414)。
在抽吸和/或净化之后,可将氧源诸如H2O的脉冲引入到腔室(步骤416)。当将氧源引入到腔室时,吡啶可协流到腔室中。吡啶和水将具有分离的入口流入腔室,以便水和吡啶不通过相同的导管和入口同时流入腔室。在将衬底暴露于氧源诸如H2O之后,可在以上所述的条件下执行其它抽吸和/或净化循环(步骤418)。
在已经抽吸和/或净化腔室之后,可测量硅酸铪层的厚度以确定是否已经达到了预定硅酸铪厚度(步骤420)。如果还没有达到预定厚度,则重复沉积工序。如果已经达到了预定厚度,则工艺终止(步骤422)。
图5是根据本发明的再一实施方式的沉积方法的流程图500。首先,将一个或多个衬底放置在工艺腔室中(步骤502)。可将铪前驱物的脉冲引入到腔室(步骤504)。氨可选地与铪前驱物用于以上所述的相似方式协流到腔室。在铪前驱物脉冲之后,可如上所述净化和/或抽吸腔室(步骤506)。
在抽吸和/或净化之后,可将氧源诸如水的脉冲引入到腔室(步骤508)。当将氧源引入到腔室时,氨可协流入腔室。水和氨可穿过不同的导管和入口或穿过相同的导管和入口协流。
在已经将氧源脉冲和氨提供到腔室之后,可如上所述再次抽吸和/或净化腔室(步骤510)。之后,硅前驱物脉冲入腔室中(步骤512)。氨可选地与硅前驱物用以上所述的方式协流入腔室。在硅前驱物脉冲之后,可再次抽吸和/或净化腔室(步骤514)。
在抽吸和/或净化之后,氧源诸如H2O的脉冲可引入到腔室(步骤516)。当将氧源引入到腔室时,氨可协流入腔室中。氨和水可如上所述流过相同或分离的导管和入口。在衬底暴露于氧源诸如H2O之后,可在以上所述的条件下执行其它抽吸和/或净化循环(步骤518)。
在已经抽吸和/或净化腔室之后,可测量硅酸铪层的厚度以确定是否已经达到了预定硅酸铪厚度(步骤520)。如果还没有达到预定厚度,则重复沉积工序。如果已经达到了预定厚度,则工艺终止(步骤522)。
应该理解,当参照处理一个衬底描述时,还可以处理多个衬底。例如,约2个衬底、约25个衬底、约50个衬底或者约100个衬底可在批处理腔室中处理。另外,吡啶浸泡可发生约1秒至约90分钟或1分钟至约20分钟的时间周期。可选地,吡啶浸泡可发生约30秒至60分钟或约20分钟至约40分钟。在又一可选实施方式中,吡啶浸泡可发生约1分钟至约40分钟。
通过提供吡啶浸泡和/或穿过分离的导管线路的吡啶和H2O协流,足够的吡啶到达腔室,并因此达到衬底表面,以确保吡啶用作催化剂。通过在H2O氧化气氛中使用吡啶用作催化剂,硅酸铪ALD可在增加的速度下在约150摄氏度到约200摄氏度的温度范围下发生。另外地,通过提供氨浸泡和/或氨与氧源协流,硅酸铪层可通过ALD在增加的速度下在约150摄氏度到约200摄氏度的温度范围下发生。
虽然前述涉及本发明的实施方式,但是在不脱离本发明的基本范围的情形下,本发明还承认其它和进一步的实施方式,并且本发明的范围由以下的权利要求书确定。
Claims (20)
1.一种高-k硅酸盐沉积方法,顺序地包含:
(a)在腔室中放置至少一个衬底;
(b)将所述至少一个衬底暴露于高-k前驱物;
(c)将所述至少一个衬底暴露于第一催化剂浸泡;
(d)将所述至少一个衬底暴露于第一氧化源;
(e)将所述至少一个衬底暴露于硅前驱物;
(f)将所述至少一个衬底暴露于第二催化剂浸泡;以及然后
(g)将所述至少一个衬底暴露于第二氧化源。
2.根据权利要求1所述的方法,其特征在于,在所述第一和第二催化剂浸泡中使用的所述催化剂选自吡啶和氨。
3.根据权利要求1所述的方法,其特征在于,所述硅前驱物选自六氯乙硅烷和四-乙氧基-硅烷。
4.根据权利要求1所述的方法,其特征在于,进一步包含:
将所述至少一个衬底暴露于净化气体。
5.根据权利要求1所述的方法,其特征在于,所述高-k前驱物是选自TDMAH、TEMAH、TDEAH和HfCl4的铪前驱物。
6.根据权利要求1所述的方法,其特征在于,进一步包含:
重复(b)-(g)步骤一次或多次。
7.根据权利要求1所述的方法,其特征在于,所述第一和第二氧化源选自H2O、O3、O2或氧自由基。
8.根据权利要求1所述的方法,其特征在于,在所述第一和第二催化剂浸泡中使用的所述催化剂是相同的。
9.根据权利要求1所述的方法,其特征在于,所述硅前驱物包含六氯乙硅烷并且所述第一和第二催化剂浸泡包含吡啶作为催化剂。
10.根据权利要求1所述的方法,其特征在于,所述硅前驱物包含四-乙氧基-硅烷并且所述第一和第二催化剂浸泡包含氨作为催化剂。
11.一种高-k硅酸盐沉积方法,顺序地包含:
(a)将至少一个衬底放置在腔室中;
(b)将所述至少一个衬底暴露于高-k前驱物;
(c)将所述至少一个衬底暴露于第一氧化源和第一催化剂,所述第一催化剂和第二氧化源经过分离的入口流入所述腔室中;
(d)将所述至少一个衬底暴露于硅前驱物;以及然后
(e)将所述至少一个衬底暴露于第二氧化源和第二催化剂,所述第二催化剂和所述第二氧化源经过分离的入口流入所述腔室中。
12.根据权利要求11所述的方法,其特征在于,所述第一和第二催化剂选自吡啶和氨。
13.根据权利要求11所述的方法,其特征在于,所述硅前驱物选自六氯乙硅烷和四-乙氧基-硅烷。
14.根据权利要求11所述的方法,其特征在于,进一步包含:
将所述至少一个衬底暴露于净化气体。
15.根据权利要求11所述的方法,其特征在于,所述高-k前驱物是选自TDMAH、TEMAH、TDEAH和HfCl4的铪前驱物。
16.根据权利要求11所述的方法,其特征在于,进一步包含:
重复(b)-(e)步骤一次或多次。
17.根据权利要求11所述的方法,其特征在于,所述第一和第二氧化源选自H2O、O3、O2或氧自由基。
18.根据权利要求11所述的方法,其特征在于,所述硅前驱物包含六氯乙硅烷并且所述第一和第二催化剂浸泡包含吡啶作为催化剂。
19.根据权利要求11所述的方法,其特征在于,所述硅前驱物包含四-乙氧基-硅烷并且所述第一和第二二催化剂浸泡包含氨作为催化剂。
20.一种高-k硅酸盐沉积方法,顺序地包含:
将至少一个衬底放置在腔室中;
将所述至少一个衬底暴露于铪前驱物;
将所述至少一个衬底暴露于水和吡啶,所述水和吡啶经过分离的入口流入所述腔室中。
将所述至少一个衬底暴露于六氯乙硅烷;以及然后
将所述至少一个衬底暴露于水和吡啶,所述水和吡啶经过分离的入口流入所述腔室中。
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2007
- 2007-11-06 KR KR1020070112577A patent/KR100954027B1/ko not_active IP Right Cessation
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- 2007-11-09 JP JP2007292450A patent/JP5219466B2/ja not_active Expired - Fee Related
- 2007-11-13 TW TW096142912A patent/TWI359877B/zh not_active IP Right Cessation
- 2007-11-14 CN CNA2007101871014A patent/CN101187012A/zh active Pending
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CN102751216A (zh) * | 2011-04-18 | 2012-10-24 | 东京毅力科创株式会社 | 热处理装置 |
CN102751216B (zh) * | 2011-04-18 | 2016-01-20 | 东京毅力科创株式会社 | 热处理装置 |
Also Published As
Publication number | Publication date |
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US7776395B2 (en) | 2010-08-17 |
KR100954027B1 (ko) | 2010-04-20 |
KR20080043706A (ko) | 2008-05-19 |
JP5219466B2 (ja) | 2013-06-26 |
TW200831696A (en) | 2008-08-01 |
TWI359877B (en) | 2012-03-11 |
US20080113096A1 (en) | 2008-05-15 |
EP1925692A1 (en) | 2008-05-28 |
JP2008142702A (ja) | 2008-06-26 |
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