CN1902738A - 高介电常数金属硅酸盐的原子层沉积 - Google Patents
高介电常数金属硅酸盐的原子层沉积 Download PDFInfo
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- CN1902738A CN1902738A CNA038257971A CN03825797A CN1902738A CN 1902738 A CN1902738 A CN 1902738A CN A038257971 A CNA038257971 A CN A038257971A CN 03825797 A CN03825797 A CN 03825797A CN 1902738 A CN1902738 A CN 1902738A
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- organic precursor
- silicon
- metal
- metal organic
- reative cell
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- 229910052914 metal silicate Inorganic materials 0.000 title claims abstract description 30
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 80
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 69
- 239000010703 silicon Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 alkyl amide Chemical class 0.000 claims abstract description 23
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 23
- 230000008676 import Effects 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 3
- 150000003950 cyclic amides Chemical class 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 31
- 238000005516 engineering process Methods 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000011109 contamination Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012212 insulator Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 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 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- QCRDVHGVAXWBFQ-UHFFFAOYSA-N C(C)[N-]C.C(C)[N-]C.C(C)[N-]C.C(C)[N-]C.[Si+4] Chemical compound C(C)[N-]C.C(C)[N-]C.C(C)[N-]C.C(C)[N-]C.[Si+4] QCRDVHGVAXWBFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical group O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PGGUBXZUXKCJBF-UHFFFAOYSA-N C(C)[N-]CC.C(C)[N-]CC.C(C)[N-]CC.C(C)[N-]CC.[Si+4] Chemical compound C(C)[N-]CC.C(C)[N-]CC.C(C)[N-]CC.C(C)[N-]CC.[Si+4] PGGUBXZUXKCJBF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 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
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- SFAIQRBEJIRKHG-UHFFFAOYSA-N n,n-dimethylformamide;silicon Chemical compound [Si].CN(C)C=O SFAIQRBEJIRKHG-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
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- 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
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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
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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Abstract
本发明涉及金属硅酸盐的高k介电层的原子层沉积(“ALD”),金属硅酸盐包括硅酸铪。更具体地,本发明涉及使用金属有机前体、硅有机前体和臭氧的金属硅酸盐的ALD形成。优选地,金属有机前体是金属烷基酰胺,和硅有机前体是硅烷基酰胺。
Description
相关申请的交叉引用
本申请涉及于2002年8月18日提交的、题为“Atomic Layer Depositionof Metal Silicates for High-k Gate and Capacitor Dielectrics”的、美国临时专利申请第60/404371号并要求优先权,其公开的全部内容在此作参照引用。本申请还涉及于2002年7月19日提交的、题为“Atomic Layer Deposition ofHigh-k Dielectric Films”的、美国临时专利申请第60/396723号,据此将其参照引用。
技术领域
本发明涉及诸如硅酸铪的金属硅酸盐的高k介电膜的原子层沉积(“ALD”)。更具体地,本发明涉及从金属有机前体、硅有机前体和臭氧形成金属硅酸盐的ALD。
背景技术
计算机的速度和功能性每年翻一倍,这在很大程度上得利于集成电路尺寸的缩减。目前,新式电路中的最小尺寸是栅极绝缘体的厚度,该栅极绝缘体使控制电极(“栅极电极”)与硅中的受控电流隔离。传统上,栅极绝缘体由二氧化硅(SiO2)和/或氮化硅(SiN)制成。这种绝缘体目前薄至20埃。然而,传统的栅极电介质在厚度减小到20埃以下时出现泄漏和可靠性故障。
因此,正在努力寻找替代的绝缘体。迄今,努力大多集中在高介电常数(高“k”)材料。如这里所使用的,如果它的介电常数“k”高于二氧化硅的介电常数(k=3.9)则该材料是“高k”。在半导体的国际技术路线图中认同了对于用在互补场效应晶体管集成的高k栅极电介质的需要。已经研究的高k电介质包括金属硅酸盐。
此外,现有技术沉积技术,例如化学气相沉积(CVD),日益不能够满足先进薄膜的要求。而CVD工艺能够满足提供阶梯覆盖得以改善的保形膜的要求,CVD工艺常常要求高处理温度,造成高杂质浓度的混入,并且具有不良的前体或反应物利用效率。例如,制作高k栅极电介质的一个障碍是在CVD工艺期间形成界面氧化硅层。另一障碍是现有技术CVD工艺限制在硅衬底上沉积用于高k栅极电介质的超薄膜。
因此,正在努力开发以纯物质方式沉积具有一致的化学计量比、厚度、保形覆盖、突变的界面、光滑的表面、以及减少的晶粒间界、裂纹和针孔的材料的改进方法。ALD是在开发的最新方法。在ALD中,通过交替的脉冲和净化,前体和共反应剂被分别引导至生长膜的表面,从而在每一脉冲周期产生膜生长的单一的单层。通过脉冲周期的总数来控制层的厚度。ALD相比于CVD具有几个优点。ALD能够在与朝更低温度发展的工业趋势相适应的相对较低的温度下进行,和能够生产保形的薄膜层。更加有利的是,ALD能够在原子尺度上控制膜厚,和能够用于“纳米工程”的复合薄膜。因此,强烈需要进一步发展ALD。
公知的是使用金属烷基酰胺作为ALD中的金属有机前体。例如,已经报道了使用四(二甲基酰胺)铪(“Hf-TDMA”)和四(乙基甲基酰胺)铪(“Hf-TEMA”)的氧化铪的ALD形成。分别参见Vapor Deposition Of MetalOxides And Silicates:Possible Gate Insulators For Future Microelectronics,R.Gordon等人,Chem.Mater.,2001,pp.2463-2464和Atomic Layer Deposition ofHafnium Dioxide Films From Hafnium Tetrakis(ethylmethylamide)And Water,K.Kukli等人,Chem.Vap.Deposition,2002,Vol.8,No.5,pp.199-204。然而,这些参考文件没有使用金属烷基酰胺来形成金属硅酸盐。而且,这些参考文献没有描述臭氧优先用作氧化剂。
臭氧是已知的氧化剂。例如,臭氧是报道的ALD工艺中的多种适合氧化剂中的一种,以从四-t-丁氧化锆制作氧化锆。参见美国专利第6465371号。然而,氧和/或蒸汽往往是金属氧化物的ALD形成中的优选氧化剂。参见,例如Atomic Layer Deposition of Hafnium Dioxide Films from Hafnium tetrakis(ethylmethylamide)And Water.
发明内容
本发明提供用于形成包括硅酸铪的高k金属硅酸盐的ALD工艺,以取代栅极和/或电容器电介质应用中的二氧化硅。该方法要求以下步骤:首先,同时或者连续地脉冲金属有机前体和硅有机前体进入包含衬底的反应室中;第二,净化反应室;第三,脉冲臭氧进入反应室;及第四,净化反应室。重复此脉冲周期直到获得目标厚度的金属硅酸盐膜。
金属有机前体可以是任何供给金属的有机材料。优选的金属有机前体包括烷基金属、金属醇盐和金属烷基酰胺。优选地,金属有机前体是金属烷基酰胺。甚至更优选地,金属有机前体是包含乙基甲基酰胺配体的金属烷基酰胺。这种前体表现出所得金属硅酸盐膜中减少的碳污染。
硅有机前体可以是任何供硅的有机材料。优选的硅有机前体包括烷基硅烷、硅醇盐、硅氧烷、硅氮烷和硅烷基酰胺。然而,优选地,硅有机前体是硅烷基酰胺。甚至更优选地,硅有机前体是四(乙基甲基酰胺)硅。再一次,这些前体表现出减少的碳污染。
通过在ALD工艺中使用臭氧,与传统的氧化剂如蒸汽相对照,所得金属硅酸盐膜中被固定和被俘获的电荷显著地减少。此外,通过在ALD工艺中使用臭氧,与传统的氧化剂如氧气相对照,ALD工艺所需的操作温度显著地降低。
按照本发明生产的高k金属硅酸盐膜用作栅极和电容器的电介质。当用作栅极电介质时,高k电介质膜在衬底(通常是硅晶片)上形成,在一个或者多个n或p掺杂沟道之间。接着,电极、例如多晶硅电极形成在该电介质之上,从而完成栅极。当用作电容器电介质时,高k电介质膜在两个导电极板之间形成。
附图说明
将参考附图详细地说明本发明,其中:
图1是概括本发明的ALD脉冲周期的流程图;以及
图2示出了在栅极中使用了按照本发明生产的高k电介质膜。
具体实施方式
本发明提供了用于形成高k金属硅酸盐的ALD工艺,从而取代栅极和/或电容器电介质中应用的二氧化硅。按照该工艺优选形成的金属硅酸盐是硅酸铪。硅酸铪表现出优越的热稳定性,因此,与其它硅酸盐相比较,导致较少的界面二氧化硅生长。
在脉冲周期开始之前,常通过位于室一端的阀,将衬底(一般是硅晶片)放置在反应室中。优选地,已经利用氟化氢清洁了硅晶片以去除生成的二氧化硅。
衬底位于可加热晶片基座上,晶片基座支撑和加热衬底至所需的反应温度。一旦衬底被适当定位,脉冲周期可以开始。
一般情况下,在脉冲周期的第一脉冲之前,晶片从约100℃被加热至约400℃范围的温度,且优选的从约200℃加热至约400℃的范围。在整个工艺中保持这个温度。
一般地,在脉冲周期的第一脉冲之前,反应室还达到约0.1至5托的压力,且优选是约0.1至2托。在整个工艺中也保持这个压力。
图1直观地示出了脉冲周期。脉冲周期包括以下步骤:
第一,挥发性液态金属有机前体和挥发性液态硅前体,或者共同地或者分别地,以及同时地或者连续地挥发和脉冲进入反应室中。然后,金属有机前体和硅源被化学吸附和/或物理吸附在衬底表面上。
通常,金属有机前体和硅前体均以约0.1至约1100标准立方厘米每分钟(“sccm”)的流速范围以约0.1至约5秒的时间导入。所述前体,或者前体混合物,可以与惰性载气,例如氩、氮或者氦气一起导入。替代方案是,所述前体,或者前体混合物,可以用纯的方式导入。优选地,前体液体被混合,然后挥发,然后与氩气一起导入反应室中。
金属有机前体可以是任何供给金属的有机材料。优选的金属有机前体包括烷基金属、金属醇盐和金属烷基酰胺。然而,优选地,金属有机前体是金属烷基酰胺。金属烷基酰胺有助于在所得膜中混入较少的碳污染。
合适的金属烷基酰胺与下面的公式相符:
M(NR1R2)n
其中“M”是金属,“R1”和“R2”独立地选自取代的或者未取代的直、支链和环状烷基,和“n”是对应于金属化合价的数。优选的,“M”是4族(Ti,Zr,Hf)金属(4族是新的周期表表示法,其对应于先前IUPAC形式的IVA族和CAS版本中的IVB族)。理想地,金属是铪。优选地,“R1”和“R2”各自是C1-C6烷基,例如甲基和乙基,因为这些配体减少了所得膜中的碳污染。甚至更加优选的,“R1”和“R2”分别是乙基和甲基单元。使用带有乙基甲基酰胺配体的金属烷基酰胺,在金属硅酸盐膜中产生较少的碳污染。例如,相对于相关的化合物,例如Hf-TDMA和四乙基酰胺铪(“Hf-TDEA”),Hf-TEMA产生较少的碳污染。
硅有机前体可以是任何供硅的有机材料。优选的硅有机前体包括烷基硅烷、硅醇盐、硅氧烷、硅氮烷和硅烷基酰胺。例如,合适的硅有机前体包括:烷基硅烷,例如四甲基硅烷;硅醇盐,例如四-t-丁氧化硅;硅氧烷,例如六甲基二硅氧烷(“HMDSO”)和四甲基二硅氧烷(“TMDSO”);以及硅氮烷,例如六甲基二硅氮烷。然而,优选的,硅有机前体是硅烷基酰胺。所述硅烷基酰胺在所得的金属硅酸盐膜中产生较少的碳含量。
合适的硅烷基酰胺包括与下面公式相符的化合物:
Si(NR1R2)4
其中“R1”和“R2”独立地选自取代的或者未取代的直、支链和环烷基。优选的,“R1”和“R2”各自是C1-C6烷基,例如甲基和乙基。甚至更加优选的,硅烷基酰胺是四(乙基甲基酰胺)硅(“Si-TEMA”),因为即使在与诸如四(二乙基酰胺)硅(“Si-TDEA”)和四(二甲基酰胺)硅(“Si-TDMA”)的类似化合物相比较时,所述化合物在金属硅酸盐膜中产生较少的碳污染。
第二,反应室通过净化去除未反应的金属有机前体、未反应的硅有机前体和副产物。净化可以例如使用惰性净化气体或者抽空净化来进行。惰性净化气体包括氩、氮和氦气。净化气体一般脉冲进入反应室中,流速从约0.1至约1100sccm,持续约0.1至约5秒的时间周期。
第三,臭氧气体脉冲进入反应室。臭氧一般以约0.1至约1100sccm的流速、持续约0.1至约5秒的时间脉冲进入反应室。臭氧可以与惰性气体例如氩、氮或者氦气一起导入。替代方案是,臭氧可以用纯的方式加入。“纯”不意味着氧气完全不存在。氧气是臭氧的前体并且几乎总是一定程度地存在于臭氧中。臭氧切断金属有机前体和硅有机前体上的配体,并加入必须的氧以形成金属硅酸盐。
通过在ALD工艺中使用臭氧,与传统的氧化剂如氧气和蒸汽相比照,所得金属硅酸盐中被固定和被俘获的电荷减少。此外,所需的操作温度降低。传统上,氧气和蒸汽一直是ALD工艺中的优选氧化剂,而臭氧一直被认为是不受欢迎的氧化剂,因为它相对高的不稳定性。然而,已经发现实际上在通过ALD形成金属硅酸盐膜时臭氧是优选的氧化剂。而氧气要求400℃左右的操作温度,臭氧允许操作温度在300℃以下。而蒸汽造成所得膜中的羟基污染,臭氧生产出不具有这种污染的膜。
第四且是最后,反应室通过净化去除未反应的臭氧和副产物。这个第二净化步骤通常按照与第一净化步骤相同的方式进行。
这样完成了ALD工艺的一个周期。最终结果是在衬底上形成金属硅酸盐的一个单层。然后,该脉冲周期重复所需的许多次数,以获得所需的膜厚度。一层接一层的ALD生长在大衬底面积上提供了极佳的覆盖,并提供了极佳的阶梯覆盖。
按照本发明优选形成的金属硅酸盐是4族金属硅酸盐,例如硅酸铪、硅酸锆和硅酸钛。最优选的金属硅酸盐是硅酸铪。硅酸铪表现出优越的热稳定性,并由此导致较少的界面二氧化硅生长。
可以通过以下方式在硅衬底上形成硅酸铪(HfxSi1-xO2)膜:脉冲Hf-TEMA和Si-TEMA的比例为1∶4的气态混合物,接着净化,然后脉冲臭氧,然后第二次净化。优选的,在整个工艺中压力是0.5托,并且气化器设定点是125℃和衬加热器处于135℃。
示范性的脉冲周期如下:首先,前体以0.04g/min的浓度和300sccm的流速持续2秒钟脉冲进入室中;第二,氩净化以300sccm的流速持续3秒钟脉冲进入室中;第三,臭氧以300sccm的流速持续2秒钟脉冲进入室中;第四且是最后,氩以300sccm的流速持续3秒钟脉冲进入室中。这些条件带来约1.5%(1σ)的均匀性和约0.95埃/周期的沉积速率。
一般地,提高晶片温度将增大沉积速率和等效厚度(Tox)并减小泄漏电流密度(Jg)。臭氧脉冲时间的增加增大了沉积速率和Tox并减小Jg。此外,已经确定所得膜中铪和硅的百分比与晶片温度相关。具体地说,随着晶片温度的上升,铪的百分比减少和硅的百分比增加。实际情况是,在晶片温度从300℃上升至400℃时,硅的百分比接近翻倍,但其后是平坦的并且直到450℃没有表现出太多的增加。例如,在350℃的晶片温度下,膜中的原子百分比是1.4%的氢、3.0%的碳、63.4%的氧、10.9%的硅、20.3%的铪和1.0%的氮。相比照,在400℃的晶片温度下,膜中的原子百分比是1.8%的氢、2.5%的碳、62.7%的氧、13.3%的硅、18.5%的铪和1.2%的氮。然而,在450℃的晶片温度下,膜中的原子百分比是1.0%的氢、2.1%的碳、63.8%的氧、13.7%的硅、18.8%的铪和0.6%的氮。
本发明的ALD工艺可以用于生产用在栅极和电容器结构中的高k电介质。例如,该工艺可以用于生产栅极,方法是在诸如掺杂硅晶片的衬底上形成高k金属硅酸盐膜并用诸如掺杂多晶硅的导电层覆盖在该结构上。替代的方案是,通过在两个导电极板之间形成高k金属硅酸盐膜,该工艺可以用于生产电容器。
图2是在栅极中使用这种高k电介质的示例。图2中,场效应晶体管100以剖面示出。晶体管包括轻p掺杂硅衬底110,其中已经形成了n掺杂硅源极130和n掺杂硅漏极140,在它们之间保留沟道区120。栅极电介质160位于沟道区120之上。栅极电极150位于栅极电介质160之上,使它仅通过中间的栅极电介质160与沟道区120分离。当源极130和漏极140之间存在电压差时,没有电流流过沟道区120,因为在源极130或者漏极140处的一个结被反向偏置。然而,通过向栅极电极150施加正电压,电流流过沟道区120。栅极电介质160是按照本发明的ALD工艺制作的高k金属硅酸盐。
本领域技术人员明白本发明的许多变化是可行的。例如,臭氧可以用多种方式产生和输送。此外,ALD室的具体布置、气体配送装置、阀、定时等常常可变化。其它在本发明精神和范围内的变化可以出现,不必在这里详细地说明。因此,本发明仅由所附权利要求的保护范围加以限制。
Claims (25)
1.一种通过原子层沉积在衬底上生长金属硅酸盐膜的方法,包括:
(i)将金属有机前体和硅有机前体导入包含衬底的反应室;
(ii)净化所述反应室;
(iii)将臭氧导入所述反应室;
(iv)净化所述反应室;以及
(v)重复步骤(i)、(ii)、(iii)和(iv),直到在该衬底上获得目标厚度的膜。
2.如权利要求1的方法,其中所述衬底是硅。
3.如权利要求1的方法,其中所述金属有机前体中的金属是4族金属。
4.如权利要求1的方法,其中所述金属有机前体中的金属是铪。
5.如权利要求1的方法,其中所述金属有机前体是直、支链和环烷基。
6.如权利要求1的方法,其中所述金属有机前体是金属烷基酰胺。
7.如权利要求1的方法,其中所述硅有机前体是硅烷基酰胺。
8.如权利要求1的方法,其中所述金属有机前体是金属醇盐。
9.如权利要求1的方法,其中所述金属有机前体和所述硅有机前体被混合、挥发和以混合气体导入所述室中。
10.如权利要求1的方法,其中所述金属有机前体和所述硅有机前体分别挥发并同时地导入所述室中。
11.如权利要求1的方法,其中所述金属有机前体和所述硅有机前体分别挥发并连续地导入所述室中。
12.一种形成用于晶体管的栅极的方法,包括:
(i)将金属有机前体和硅有机前体导入包含衬底的反应室;
(ii)净化所述反应室;
(iii)将臭氧导入所述反应室;
(iv)净化所述反应室;
(v)重复步骤(i)、(ii)、(iii)和(iv),直到在衬底上获得目标厚度的介电膜;以及
(vi)将导电膜设置在所述介电膜之上。
13.如权利要求12的方法,其中所述衬底是硅。
14.如权利要求12的方法,其中所述金属有机前体是4族金属的直、支链和环酰胺和其中所述硅有机前体是供硅的有机材料。
15.如权利要求12的方法,其中所述金属有机前体是4族金属的金属烷基酰胺,和其中所述硅有机前体是硅烷基酰胺。
16.如权利要求12的方法,其中所述金属有机前体和所述硅有机前体被混合、挥发和以混合气体导入所述室中。
17.如权利要求12的方法,其中所述金属有机前体和所述硅有机前体分别挥发并同时地导入所述室中。
18.如权利要求12的方法,其中所述金属有机前体和所述硅有机前体分别挥发并连续地导入所述室中。
19.一种形成电容器的方法,包括:
(i)将金属有机前体和硅有机前体导入包含衬底的反应室;
(ii)净化所述反应室;
(iii)将臭氧导入所述反应室;
(iv)净化所述反应室;
(v)重复步骤(i)、(ii)、(iii)和(iv),直到在衬底上获得目标厚度的介电膜;以及
(vi)使所述膜位于两个电极之间。
20.如权利要求19的方法,其中所述衬底是所述两个电极中的一个。
21.如权利要求19的方法,其中所述金属有机前体是4族金属的直、支链和环酰胺和其中所述硅有机前体是供硅的有机材料。
22.如权利要求19的方法,其中所述金属有机前体是4族金属的金属烷基酰胺,和其中所述硅有机前体是硅烷基酰胺。
23.如权利要求19的方法,其中所述金属有机前体和所述硅有机前体被混合、挥发和以混合气体导入所述室中。
24.如权利要求19的方法,其中所述金属有机前体和所述硅有机前体分别挥发并同时地导入所述室中。
25.如权利要求19的方法,其中所述金属有机前体和所述硅有机前体分别挥发并连续地导入所述室中。
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2003
- 2003-08-15 TW TW092122538A patent/TW200408015A/zh unknown
- 2003-08-18 KR KR1020057002824A patent/KR20050059077A/ko active IP Right Grant
- 2003-08-18 JP JP2004529512A patent/JP2005536064A/ja active Pending
- 2003-08-18 WO PCT/US2003/025739 patent/WO2004017378A2/en active Application Filing
- 2003-08-18 CN CNA038257971A patent/CN1902738A/zh active Pending
- 2003-08-18 AU AU2003259879A patent/AU2003259879A1/en not_active Abandoned
- 2003-08-18 US US10/525,122 patent/US20060228888A1/en not_active Abandoned
- 2003-08-18 EP EP03788581A patent/EP1535320A4/en not_active Withdrawn
Cited By (3)
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US9184061B2 (en) | 2002-08-28 | 2015-11-10 | Micron Technology, Inc. | Systems and methods for forming zirconium and/or hafnium-containing layers |
CN102191479A (zh) * | 2010-02-04 | 2011-09-21 | 气体产品与化学公司 | 制备含硅膜的方法 |
CN115838916A (zh) * | 2015-10-16 | 2023-03-24 | Asm Ip控股有限公司 | 用于栅极介电质的原子层沉积的实施方法 |
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WO2004017378A3 (en) | 2004-05-06 |
AU2003259879A1 (en) | 2004-03-03 |
EP1535320A4 (en) | 2006-11-15 |
US20060228888A1 (en) | 2006-10-12 |
JP2005536064A (ja) | 2005-11-24 |
AU2003259879A8 (en) | 2004-03-03 |
EP1535320A2 (en) | 2005-06-01 |
WO2004017378A2 (en) | 2004-02-26 |
KR20050059077A (ko) | 2005-06-17 |
TW200408015A (en) | 2004-05-16 |
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