CN1626699A - 钨金属去除液以及使用了该去除液的钨金属的去除方法 - Google Patents
钨金属去除液以及使用了该去除液的钨金属的去除方法 Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 98
- 239000010937 tungsten Substances 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 86
- 239000002184 metal Substances 0.000 title claims abstract description 86
- 239000007788 liquid Substances 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims abstract description 43
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 238000005530 etching Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229910052814 silicon oxide Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 210000004379 membrane Anatomy 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 210000000721 basilar membrane Anatomy 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 235000012976 tarts Nutrition 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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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
- H01L21/02041—Cleaning
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- 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
- H01L21/02041—Cleaning
- H01L21/02082—Cleaning product to be cleaned
- H01L21/02087—Cleaning of wafer edges
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- 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
- H01L21/02041—Cleaning
- H01L21/02082—Cleaning product to be cleaned
- H01L21/0209—Cleaning of wafer backside
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
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Abstract
本发明提供一种用于去除在半导体基板上成膜或者附着的不需要的钨金属的稳定的酸性去除液以及使用了该去除液的钨金属的去除方法。本发明所述的去除液含有原高碘酸以及水。
Description
技术领域
本发明涉及用于有效地去除在半导体基板等上成膜或者附着的不需要的钨金属的去除液,详细地是涉及对基板底面的硅以及作为基底膜的氮化钛、氧化硅的腐蚀性小的钨金属去除液、以及使用了该去除液的钨金属的去除方法。
背景技术
例如特开昭62-143422号公报报告了作为半导体的门电极材料的钨硅化物和热处理后基本上就视作钨金属而使用的例子。例如特开平8-250462号公报报告了作为半导体的布线而使用了钛钨和钛铝合金。另外,例如特开平8-250462号公报还报告了随着半导体基板的多层化,作为埋入接触孔和微通孔用金属而使用钨金属,并且在将钨金属埋入接触孔和微通孔后,对基板表面上成膜的钨金属进行加工后作为布线使用。
近几年来,钨金属用作为DRAM、FeRAM、***LSI等电极材料被加以利用。钨金属的成膜方法有溅射法以及CVD方法,不管哪种方法,在包括周缘部的基板上整体进行钨金属成膜。考虑到在元件形成区域以外的基板的周缘部以及底面成膜或者附着的钨金属容易自然剥离,剥离后的钨金属附着在元件形成部,或由于通过搬运***可能引起成膜装置的交叉污染,所以在移至下一个工序之前,一直在研究把元件形成区域以外的基板的周缘部以及底面的成膜或者附着的钨金属彻底去除。这里所说的“元件形成区域以外的区域”是指除了半导体基板的端面以及底面外,包括元件形成面的周缘部的区域。
到现在为止没有发现关于去除在元件形成区域以外的基板周缘部以及底面成膜或者附着的钨金属的报告,但有钨金属或者钨金属合金的蚀刻液的报告。
例如特开平8-250462号公报、特开平11-219946号公报、特开2000-311891号公报提出了用过氧化氢或过氧化氢水同氨与水的混合液作为钨金属的蚀刻液,但是存在过氧化氢水释放氧气而易分解的蚀刻液的寿命短暂的问题。另外由于这些蚀刻液在蚀刻后产生粒状和膜状的残渣等,所以绝对说不上是一种实用的蚀刻液。因此,这些作为钨金属的去除液并不适合。
另外,在半导体元件的制造过程中,氧化硅绝缘膜以及钨金属膜在硅基板端面以及底面上呈层合的状态,去除钨金属膜的工序和去除氧化硅的工序在同一装置中进行,去除氧化硅膜通常使用氢氟酸等酸性试剂。因此如果使用含有氨等碱性试剂来去除钨金属,就会出现蚀刻室和排气管内析出氟化铵等盐的问题。
特开平8-250462号公报报告了作为用于为了防止盐的析出的酸性的钨金属去除液,考虑用含有氢氟酸和硝酸的水溶液,但这种水溶液也可以腐蚀硅、氧化硅,所以不适合用在电子元件的制造中。
另一方面,特开2001-68463号公报报告了去除金属的对象不同,但作为去除在半导体基板周缘部成膜或者附着的钌金属的酸性去除液的含有原高碘酸和硝酸的组合物。但是关于钨金属的去除没有任何公开。
并且,美国专利第6461978号报告了作为本发明类似的组合物,含有氟化氢、过碘酸和硫酸的蚀刻液,但其没有公开有关不含硫酸的蚀刻液。
发明内容
因此,本发明所要解决的课题是提供为去除半导体基板上成膜或附着的不需要的钨金属、稳定且为酸性的去除液,和使用了该去除液的钨金属的去除方法。
本发明者们为了解决上述课题通过反复专心研究,最后发现含有原高碘酸和水的去除液,可以充分地溶解和去除钨金属,从而完成了本发明。
即,本发明涉及在硅半导体基板上成膜或附着的钨金属的去除液,所述去除液中含有原高碘酸、氢氟酸和水,且不含有硫酸。
另外,本发明涉及所述去除液中原高碘酸的含量为5~50质量%,且氢氟酸的含量为0.01~5质量%。
另外,本发明涉及所述去除液中钨金属为在半导体的元件形成区域以外的区域成膜或附着的钨金属。
并且,本发明涉及一种钨金属的去除方法,其是将钨金属成膜的半导体基板保持水平并旋转,在该半导体基板的元件形成区域以外,通过喷涂上述去除液,去除在该半导体元件形成区域以外的区域成膜或附着的钨金属。
作为本发明的去除液,如果使用特开2001-68463号公报所记载的钌金属去除液的所知的硝酸作为必要成分,钨金属的蚀刻率就会降低从而不能获得充分地溶解和去除效果。公知的去除液,提高附着在半导体基板上的钌金属的蚀刻率,而降低同样是过渡金属的钨金属的蚀刻率,在本发明中吃惊地发现氢氟酸具有显著的钨金属去除效果。
本发明的钨金属的去除液,对硅以及基底膜氮化钛、氧化硅的腐蚀性弱,可以充分地溶解和去除不需要的钨金属。特别适合去除在半导体基板的周围以及底面成膜或附着的不需要的钨金属。通过使用本发明的钨金属去除液,可以去除不需要的钨金属,并且可以对提高半导体制造的成品率作出贡献。
本发明的去除液,即使是由原高碘酸和水组成,也能以充分地溶解速度除去钨金属,而进一步通过添加氢氟酸就可以大幅度提高钨金属的去除功效。并且本发明的去除液,通过调节氢氟酸的含量可以抑制对硅以及作为基底膜的氧化硅或者氮化钛的溶解,从而可以有选择地只去除钨金属。
另外,本发明的去除液具有优良的稳定性,所以可以长期保存。并且本发明的去除液不会产生蚀刻后的粒状或者膜状的残渣,还由于可以和其它酸性的液体在同一装置内效率较好地使用,所以是一种非常实用的蚀刻液体。
附图说明
图1是表示钨金属膜成膜后的硅基板的外观图。
图2是表示钨金属膜成膜后的硅基板的外观图。
图3是说明使用去除液去除钨金属的方法的图。
符号说明:
1 表示硅基板
2、2’表示钨膜
3 表示绝缘膜
5 表示基板承载台
具体实施方式
以下就本发明的实施方式进行阐述。
作为与本发明去除液成分的原高碘酸类似的化合物有高氯酸、过硫酸、溴酸、过氧化氢水等,但是高氯酸、过硫酸得不到钨金属充分地溶解和去除效果。另外,溴酸稳定性差,过氧化氢水如前所述由于自身分解所以很难使用。与此相对,原高碘酸可以充分溶解、去除钨金属,并且,由于不含碱性金属,对元件的不良影响甚小,所以比较理想。
作为和本发明去除液的成分的氢氟酸相同的无机酸,例如有铝以及铝合金的蚀刻液中使用的硝酸、盐酸、醋酸、磷酸等等,但是即使将磷酸、硝酸、醋酸添加到原高碘酸中,和单独使用原高碘酸相比,并没有出现协同效果,不能产生充分地溶解和去除钨金属的效果。当盐酸和原高碘酸混合时,会产生气体,不具有实用性。由于发现添加氢氟酸和单独用原高碘酸相比,具有协同效果式的显著的对钨金属的去除的效果,所以是优选的。
在本发明中,虽然对钨金属的溶解速度并不作特别限定,但是从作为钨金属去除液的处理时间的观点来看,为30nm/min或以上,优选100nm/min或以上,更优选200nm/min或以上。
在本发明中,对原高碘酸的含量,只要能够达到将钨金属充分溶解和去除的程度即可,不作特别限制,但是优选将其含量控制在能有效地防止原高碘酸的析出的程度,所以典型的为5~50质量%,优选为15~30质量%。
在本发明中,虽然对氢氟酸的含量只要达到可以充分溶解和去除钨金属的程度即可,不作特别限制,但是优选能够达到防止对底面的硅、基底的氮化钛、氧化硅进行腐蚀的程度的量,所以典型的为0~5质量%,优选的为0.01~5质量%,更优选的为0.1~1质量%。
本发明的去除液除了原高碘酸、氢氟酸以外,通常含水构成。
通过本发明的去除液,处理温度越高钨金属的溶解速度就越快,但是当处理温度过高时,会出现由于喷射高温的水溶液通过蒸发而引起原高碘酸的析出以及液体组成的变化,而当处理温度过低时,由于不能获得对钨金属的充分地去除性性能,所以要对温度进行适度地调整。优选温度为30℃~60℃,更优选的是40℃~50℃。
另外,本发明的去除液,在不损害去除性性能的范围内可以添加表面活性剂等各种添加剂和水溶性有机溶剂。
作为本发明的优选实施方案,可以是举出如下构成形态:由原高碘酸组成的水溶液,由原高碘酸和氢氟酸组成的水溶液,或者在其中添加少量表面活性剂等添加剂。
本发明的去除液,除了作为去除在半导体基板上成膜或者附着的不需要的钨金属的去除液,也可以用作钨电极布线的微细加工(布线图案的制作)用途的蚀刻液体。
本发明的去除液,特别是用在元件形成区域以外的区域成膜或者附着了钨金属的半导体基板的清洗中是有效的。例如,在半导体基板的元件形成区域上钨金属成膜后,在清洗去除元件形成区域以外的区域上成膜或附着的钨金属时具有显著的效果。
下面,就关于使用去除在硅基板的元件形成区域以外的区域上成膜或附着的钨金属的去除液的处理进行说明。图1是表示钨金属膜形成后的基板的状态。硅基板1放置在基板承载台5上的状态。通过CVD法形成钨膜2时,在硅基板1的端面以及底面有钨成膜或附着。另外,如图2所示,形成绝缘膜和底膜后,当钨膜形成时,同样地在硅基板的端面以及底面由于有钨膜成膜或附着,使用本发明的去除液是有效的。
在使用本发明的去除液对钨金属进行去除时,希望去除液不要接触元件形成区域。例如,如图3所示,通过旋转清洗来进行钨金属的去除,可以一边对元件形成面喷涂氮气等惰性气体,一边使去除液去只接触硅基板的端面以及底面。
实施例
以下通过列举实施例和比较例来进一步详细地说明本发明,但本发明并不限于这些实施例。
实施例1
将在硅基板上成膜的钨金属(膜厚500nm)切成约15mm的矩形薄片,做成试样。将该试样浸泡在本发明的去除液中,处理温度为50℃。把使用本发明的去除液的组成如表1所示。各成分的含量用相对于全部去除液的质量%的值表示。剩余部分是水。浸泡到钨金属膜消失为止,从直到钨金属膜消失所需时间来求出钨金属的溶解速度。其结果示于表1,2及表3中。表中的溶解速度为nm/min。
从表1~3显示的结果,可以判断原高碘酸、或者原高碘酸和氢氟酸组合时具有显著的钨金属的去除效果。
[表1]
原高碘酸(质量%) | 氢氟酸(质量%) | 溶解速度(nm/min) | |
No.1 | 1 | - | - |
No.2 | 5 | - | 51 |
No.3 | 15 | - | 106 |
No.4 | 30 | - | 162 |
No.5 | 50 | - | 150 |
No.6 | 5 | 0.1 | 75 |
No.7 | 5 | 0.5 | 206 |
No.8 | 5 | 1 | 211 |
No.9 | 15 | 0.1 | 150 |
No.10 | 15 | 0.5 | 278 |
No.11 | 15 | 1 | 288 |
No.12 | 30 | 0.1 | 204 |
No.13 | 30 | 0.5 | 337 |
No.14 | 30 | 1 | 341 |
No.15 | 40 | 0.5 | 339 |
[表2]
原高碘酸(质量%) | 硝酸(质量%) | 盐酸(质量%) | 醋酸(质量%) | 溶解速度(nm/min) | |
No.16 | 30 | 5 | 92 | ||
No.17 | 30 | 5 | - | ||
No.18 | 30 | 5 | 117 |
No.17由于去除液调制时没有产生气体,所以没有进行评估。
[表3]
高氯酸(质量%) | 过硫酸铵(质量%) | 硝酸铈(IV)铵(质量%) | 硝酸(质量%) | 溶解速度(nm/min) | |
No.19 | 30 | 10 | 0 | ||
No.20 | 30 | 10 | 0 | ||
No.21 | 30 | 10 | 0 |
实施例2
将硅基板上成膜的钨金属(膜厚500nm)切成5mm的矩形薄片,做成试样。将该样浸泡在本发明的去除液中,将去除液用搅拌器搅拌和不搅拌时,别求出在30℃、40℃及50℃时的溶解速度。使用的去除液的组成示于表4中。各成分的含量用相对于全部去除液的质量%的值表示。剩余部分为水。浸泡到钨金属膜消失为止,从直到钨金属膜消失所需时间来求出钨金属的溶解速度。其结果示于表4中。另外,表中的溶解速度的单位为nm/min。
已经很明确通过搅拌钨金属的溶解速度会变快。为此,在发生物理作用的旋转清洗中,和浸渍法相比可以期待迅速地去除钨金属。
表4是在30℃、40℃和50℃时的各自温度下通过浸渍法表示的溶解速度。表示了温度越高溶解速度越快,但是本发明的钨去除液是在基板的元件形成区域以外的区域通过喷射去除液进行的,所以如果处理温度过高,会由于蒸发出现原高碘酸的析出以及液体组成的变化。另外处理温度过低,就不能获得对钨金属的充分地去除性能,所以优选温度为30℃~60℃,更优选的温度为40℃~50℃。
[表4]
原高碘酸(质量%) | 氢氟酸(质量%) | 搅拌 | 温度/溶解速度(nm/min) | |||
30℃ | 40℃ | 50℃ | ||||
No.1 | 30 | - | 无有 | 2930 | 9091 | 162164 |
No.2 | 30 | 0.1 | 无有 | 4049 | 108126 | 204246 |
No.3 | 30 | 0.5 | 无有 | 5565 | 142169 | 337380 |
No.4 | 30 | 1.0 | 无有 | 5565 | 143169 | 341390 |
No.5 | 40 | 0.5 | 无有 | 5463 | 140167 | 339380 |
实施例3
将在硅基板上成膜的氧化硅、氮化钛作为试样,求出在50℃中的氮化钛、氧化硅的溶解速度。结果示于表5和表6中。一般来说优选钨金属和基底的氧化硅、氮化钛的蚀刻的选择比为10或以上,但是在本发明中,和钨金属的溶解速度相比,氧化硅、氮化钛的溶解速度大幅度降低,很明显蚀刻选择比为10或以上。为此,我们可知本发明的去除液是对于作为钨金属基底膜的氮化钛和氧化硅的腐蚀小,非常实用的去除液。
[表5]
W去除液,通过(HF+H5IO6)的SiO2蚀刻率(液体温度50℃、搅拌浸渍)
HF(wt%) | H5IO6(wt%) | W蚀刻率(nm/min) | SiO2蚀刻率(nm/min) | 蚀刻选择比(W率/SiO2率) |
- | 30 | 164 | 0 | - |
0.1 | 30 | 246 | 0.7 | 351 |
0.2 | 30 | 278 | 3 | 93 |
0.3 | 30 | 330 | 5 | 66 |
0.5 | 30 | 380 | 9 | 42 |
1.0 | 30 | 390 | 21 | 19 |
通过干涉式膜厚计测定SiO2蚀刻率。
[表6]
W去除液,通过(HF+H5IO6)的TiN蚀刻率(液体温度50℃、搅拌浸渍)
HF(wt%) | H5IO6(wt%) | W蚀刻率(nm/min) | TiN蚀刻率(nm/min) | 蚀刻选择比(W率/TiN率) |
- | 30 | 164 | 0 | - |
0.1 | 30 | 246 | 5↓ | 50↑ |
0.2 | 30 | 278 | 5↓ | 50↑ |
0.3 | 30 | 330 | 5 | 66 |
0.5 | 30 | 380 | 8 | 48 |
1.0 | 30 | 390 | 14 | 28 |
通过目测测定TiN蚀刻率。
通过使用本发明的钨金属去除液,可以充分溶解和去除在元件形成区域以外的基板周缘部和其它部分成膜或附着的钨金属,可以对提高半导体制造的成品率作出贡献。
Claims (4)
1、一种在半导体基板上成膜或附着的钨金属的去除液,其中所述去除液含有原高碘酸、氢氟酸和水,且不含有硫酸。
2、根据权利要求1所记载的去除液,其中所述原高碘酸的含量为5~50质量%,且氢氟酸的含量为0.01~5质量%。
3、根据权利要求1或者2所记载的去除液,所述钨金属为半导体基板的元件形成区域以外的区域上成膜或附着的钨金属。
4、一种在该半导体基板的元件形成区域以外的区域上成膜或附着的钨金属的去除方法,其是通过将钨金属成膜的半导体基底保持水平并旋转,在该半导体基板的元件形成区域以外的区域上喷涂权利要求1所记载的去除液。
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CN103484864A (zh) * | 2012-06-11 | 2014-01-01 | 北大方正集团有限公司 | 钨层去除溶液 |
CN108130535A (zh) * | 2016-12-01 | 2018-06-08 | 添鸿科技股份有限公司 | 钛钨合金的蚀刻液 |
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KR20050110470A (ko) * | 2004-05-19 | 2005-11-23 | 테크노세미켐 주식회사 | 반도체 기판용 세정액 조성물, 이를 이용한 반도체 기판세정방법 및 반도체 장치 제조 방법 |
KR20050116739A (ko) * | 2004-06-08 | 2005-12-13 | 동부아남반도체 주식회사 | 기판 상의 금속막 스트립 방법 |
US7790624B2 (en) * | 2008-07-16 | 2010-09-07 | Global Foundries Inc. | Methods for removing a metal-comprising material from a semiconductor substrate |
JP5854230B2 (ja) * | 2012-12-13 | 2016-02-09 | 栗田工業株式会社 | 基板洗浄液および基板洗浄方法 |
JP6460729B2 (ja) * | 2014-10-31 | 2019-01-30 | 富士フイルム株式会社 | 基板処理方法、及び、半導体素子の製造方法 |
WO2016068183A1 (ja) * | 2014-10-31 | 2016-05-06 | 富士フイルム株式会社 | ルテニウム除去組成物、及び、磁気抵抗メモリの製造方法 |
JP6769760B2 (ja) | 2016-07-08 | 2020-10-14 | 関東化学株式会社 | エッチング液組成物およびエッチング方法 |
JP6941959B2 (ja) * | 2017-03-31 | 2021-09-29 | 関東化学株式会社 | エッチング液組成物およびエッチング方法 |
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KR100271769B1 (ko) * | 1998-06-25 | 2001-02-01 | 윤종용 | 반도체소자의 제조방법, 이를 위한 반도체소자 제조용 식각액조성물 및 반도체소자 |
US6232228B1 (en) * | 1998-06-25 | 2001-05-15 | Samsung Electronics Co., Ltd. | Method of manufacturing semiconductor devices, etching composition for manufacturing semiconductor devices, and semiconductor devices made using the method |
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CN103484864B (zh) * | 2012-06-11 | 2016-04-27 | 北大方正集团有限公司 | 钨层去除溶液 |
CN108130535A (zh) * | 2016-12-01 | 2018-06-08 | 添鸿科技股份有限公司 | 钛钨合金的蚀刻液 |
CN108130535B (zh) * | 2016-12-01 | 2020-04-14 | 添鸿科技股份有限公司 | 钛钨合金的蚀刻液 |
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C56 | Change in the name or address of the patentee | ||
CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Co-patentee after: Renesas Electronics Corporation Patentee after: Kanto Kagaku K. K. Address before: Tokyo, Japan Co-patentee before: NEC Corp. Patentee before: Kanto Kagaku K. K. |
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C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090722 Termination date: 20131202 |