CN109423290A - 用于在制造半导体器件过程中相对于氮化钛选择性地去除氮化钽的蚀刻溶液 - Google Patents
用于在制造半导体器件过程中相对于氮化钛选择性地去除氮化钽的蚀刻溶液 Download PDFInfo
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- CN109423290A CN109423290A CN201810980639.9A CN201810980639A CN109423290A CN 109423290 A CN109423290 A CN 109423290A CN 201810980639 A CN201810980639 A CN 201810980639A CN 109423290 A CN109423290 A CN 109423290A
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000005530 etching Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000004065 semiconductor Substances 0.000 title description 16
- 239000000203 mixture Substances 0.000 claims abstract description 95
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000004377 microelectronic Methods 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- -1 tetrabutyl ammonium tetrafluoroborate Chemical compound 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims description 2
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- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000000243 solution Substances 0.000 description 22
- 235000011007 phosphoric acid Nutrition 0.000 description 18
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229920005591 polysilicon Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 229910021417 amorphous silicon Inorganic materials 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02046—Dry cleaning only
-
- 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
- H01L21/04—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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
- H01L21/04—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
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Abstract
本文描述了一种蚀刻溶液,其包含水;磷酸溶液(水性);氟离子源;和水混溶性有机溶剂。该组合物可用于在制造其上具有氮化钽和氮化钛材料的微电子器件的过程中从该微电子器件中相对于氮化钛而选择性地去除氮化钽。
Description
相关申请的交叉引用
本申请要求2017年8月25日提交的美国临时申请62/550,474的优先权,其全部内容出于所有允许的目的通过引用并入本文。
技术领域
本发明涉及用于制造半导体器件的水性蚀刻溶液。更具体地,本发明提供一种水性蚀刻溶液,其表现出在复合半导体器件中相对于氮化钛膜增加的对氮化钽膜的蚀刻选择性。
背景技术
随着半导体工业已经发展到纳米技术工艺节点以追求更高的器件密度、更高的性能和更低的成本,制造和设计方面的挑战已导致三维设计的发展,例如Fin FET。Fin FET器件是一种多栅结构,其通常包括具有高纵横比的半导体鳍,并且其中形成半导体晶体管器件的沟道和源/漏区。利用该沟道和源/漏区的增加的表面积的优点,在鳍结构的侧面上并沿着鳍结构的侧面形成栅(例如,包绕),以产生更快、更可靠和更好控制的半导体晶体管器件。在一些器件中,Fin FET器件的源/漏区中的应变材料利用例如磷掺杂的含硅外延分层。
栅叠层通常包括:第一层非晶硅或多晶体硅(通常称为多晶硅),其是未掺杂的,形成在栅介电层的顶表面上;第二层多晶硅或非晶硅,其为n型的,形成在未掺杂的多晶硅或非晶硅层的顶表面上,以在栅中建立所需的功函数;金属层,其处于压应力下,在第二多晶硅或非晶硅层的顶表面上形成;和第三层多晶硅或非晶硅,其在金属层的顶表面上形成,以提供用于随后形成金属硅化物的硅表面。经受压应力的金属可以是氮化钛(TiN),氮化钽(TaN),钨(W),钼(Mo)或另一金属,其在NMOS晶体管的沟道区域中产生拉伸应力,减少掺杂剂在下层多晶硅或非晶硅和上层多晶硅或非晶硅之间的扩散,并且与IC制造中使用的退火工艺相容。在包括NMOS和PMOS晶体管的互补金属氧化物半导体(CMOS)IC中,n型多晶硅层和金属层在NMOS晶体管区域中被图案化,而第一多晶硅或非晶硅层和第三多晶硅或非晶硅层在NMOS和PMOS晶体管区域两者中被图案化。通常采用蚀刻工艺来减小NMOS和PMOS晶体管的栅叠层之间的高度差异,以便于栅图案光刻处理。
当Finfet金属栅结构采用TaN和TiN二者以实现某些功能时,通常需要相对于一种材料而蚀刻另一种材料。例如,在制造一些NMOS器件期间,有必要蚀刻TaN并在TiN处停止,但是使用常规的湿法蚀刻组合物很难在TiN上停止。通常,增加氧化剂的组成例如提高TaN的蚀刻速率,但也提高了TiN的蚀刻速率并损坏该层。因此,本领域需要一种可以相对于TiN而选择性地蚀刻TaN的湿法蚀刻化学作用。
发明内容
在一个方面,本发明提供一种适合于从微电子器件中相对于TiN而选择性地去除TaN的蚀刻溶液,所述蚀刻溶液包含:水;含磷无机酸或其盐;氟离子源;和水混溶性有机溶剂。
在另一个方面,本发明提供一种适合于从微电子器件中相对于TiN而选择性地去除TaN的蚀刻溶液,所述蚀刻溶液包含:水;磷酸或其盐;氟离子源;和水混溶性有机溶剂。
在另一个方面,提供了一种蚀刻组合物,所述蚀刻组合物包含:水;约0.5重量%至约50重量%的所述含磷无机酸(纯);约0.01重量%至约20重量%的氟离子源(纯);和约1重量%至约50重量%的水混溶性有机溶剂。
在另一个方面,提供了一种蚀刻组合物,所述蚀刻组合物包含:水;约0.5重量%至约35重量%或约1重量%至约25重量%的所述含磷无机酸(纯);约0.01重量%至约10重量%或约0.1重量%至约10重量%的氟离子源(纯);和约1重量%至约40重量%或约1重量%至约30重量%的水混溶性有机溶剂。或者,本发明的组合物可以以下述的任何量、以下述量的任何组合包含这些和其它组分。
在另一个方面,本发明提供了一种在包含TaN和TiN的微电子器件上相对于TiN而选择性地提高TaN的蚀刻速率的方法,该方法包括以下步骤:使所述包含TaN和TiN的微电子器件与水性组合物接触,所述水性组合物包含:水;含磷无机酸或其盐或者磷酸或其盐;氟离子源;和水混溶性有机溶剂;和在所述氮化钽被至少部分地去除之后冲洗所述微电子器件,其中氮化钽相对于氮化钛的蚀刻选择性大于3或大于5或大于8或大于10或大于15或大于25或大于30。本发明的任何组合物均可用于本发明的方法中。在一些实施方式中,可能期望提供小于或小于或小于或小于或小于的TiN蚀刻速率。
本发明的实施方式可以单独使用或彼此组合使用。
附图说明
图1是XPS分析的图,其显示本发明的组合物在40℃下3分钟后去除了大部分TaN层。
具体实施方式
本文引用的所有参考文献,包括公开出版物、专利申请和专利均通过引用并入本文,其程度如同每个参考文献被单独且具体地表明通过引用并入并且在本文中以其全文阐述。
在描述本发明的上下文中(特别是在以下权利要求的上下文中)使用术语“一个”和“一种”和“所述”以及类似的指代应被解释为涵盖单数和复数二者,除非本文另有说明或与上下文明显矛盾。除非另有说明,否则术语“包含”、“具有”、“包括”和“含有”应被解释为开放式术语(即,意味着“包括但不限于”)。除非本文另有说明,否则本文中对数值范围的描述仅旨在用作单独提及落入该范围内的每个单独值的简写方法,并且每个单独的值并入本说明书中,如同其在本文中被单独记载一样。除非本文另有说明或上下文明显矛盾,否则本文所描述的所有方法均可以任何合适的顺序进行。除非另外声明,否则本文提供的任何和所有实例或示例性语言(例如,“诸如”)的使用仅旨在更好地说明本发明,而不是对本发明的范围进行限制。说明书中的任何语言都不应被解释为表明任何未要求保护的要素对于本发明的实施是必不可少的。在说明书和权利要求中使用术语“包含”包括“基本上由......组成”和“由......组成”的较窄语言。
本文描述了本发明的实施方式,包括发明人已知的实施本发明的最佳方式。在阅读前面的描述后,那些实施方式的变化对于本领域普通技术人员而言将变得显而易见。发明人预期技术人员会适当地采用这些变化,并且发明人意指本发明可以不同于本文具体描述的方式实施。因此,本发明包括适用的法律允许的所附权利要求中所述主题的所有改变和等价物。此外,除非本文另有说明或上下文明显矛盾,否则本发明涵盖上述要素以其所有可能变型的任何组合。
本发明一般涉及可用于在制造其上具有TaN和TiN的微电子器件的过程中从该微电子器件中相对于TiN而选择性地去除TaN的组合物。
应理解,作为材料沉积在微电子器件上的术语“硅”将包括多晶硅。
为了便于参考,“微电子器件”或“半导体器件”对应于半导体衬底(例如晶片)、平板显示器、相变存储器件、太阳能电池板和其他产品,包括太阳能衬底、光伏器件和微机电系统(MEMS),其制造用于微电子、集成电路或计算机芯片应用。太阳能衬底包括但不限于硅、非晶硅、多晶硅、单晶硅、CdTe、铜铟硒化物、铜铟硫化物和镓上的砷化镓。太阳能衬底可以是掺杂的或未掺杂的。应理解,术语“微电子器件”并不旨在以任何方式进行限制,并且包括最终将成为微电子器件或微电子组件的任何衬底。
“复合半导体器件”或“复合微电子器件”是指该器件具有存在于非导电衬底上的多于一种材料和/或层和/或层部分。所述材料可包括高K电介质、和/或低K电介质和/或屏障材料和/或覆盖材料(capping material)和/或金属层和/或本领域技术人员已知的其他材料。
如本文所定义,“低k介电材料”对应于用作分层微电子器件中的介电材料的任何材料,其中该材料具有小于约3.5的介电常数。优选地,低k介电材料包括低极性材料,例如含硅有机聚合物、含硅杂化有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和碳掺杂氧化物(CDO)玻璃。应理解,低k介电材料可具有不同的密度和不同的孔隙率。
如本文所定义,“高k介电材料”是指具有高介电常数k(与二氧化硅相比)的材料。高k电介质可用于代替微电子器件的二氧化硅栅电介质或另一电介质层。高k材料可以是二氧化铪(HfO2)、氧氮化铪(HfON)、二氧化锆(ZrO2)、氧氮化锆(ZrON)、氧化铝(Al2O3)、氧氮化铝(AlON)、氧化铪硅(HfSiO2)、氧化铪铝(HfAlO)、氧化锆硅(ZrSiO2)、二氧化钽(Ta2O5)、氧化铝、Y2O3、La2O3、氧化钛(TiO2)、铝掺杂二氧化铪,铋锶钛(BST)或铂锆钛(PZT)。
如本文所定义,术语“屏障材料”对应于本领域中用于密封金属线(例如铜互连)的任何材料,以使所述金属(例如铜)到介电材料中的扩散最小化。优选的屏障层材料包括钽、钛、钌、铪和其他难熔金属及其氮化物和硅化物。
“基本上不含”在本文中定义为小于0.001重量%。“基本上不含”还包括0.000重量%。术语“不含”是指0.000重量%。
如本文所用,“约”旨在对应于所述值的±5%。
在所有这样的组合物中,其中组合物的特定组分参照包括零下限的重量百分比范围来讨论,应理解,这些组分可在组合物的各种具体实施方式中存在或不存在,并且在其中存在这些组分的情况下,它们可以以基于采用这些组分的组合物的总重量低至0.001重量%的浓度存在。请注意,组分的所有百分比均为重量百分比并且基于组合物的总重量,即100%。
在该方面的广泛实践中,本发明的蚀刻溶液包含以下、基本上由以下组成或由以下组成:水;磷酸溶液(水性);氟离子源;和水混溶性有机溶剂。
在一些实施方式中,本文公开的蚀刻溶液组合物被配制成基本上不含氧化剂,例如过氧化物。因此,在一些实施方式中,蚀刻溶液组合物不含过氧化氢。
本文采用的标题不旨在限制;相反,它们仅出于组织目的而包括在此。
水
本发明的蚀刻组合物是水基的,且因此包含水。在本发明中,水以各种方式起作用,例如,用于溶解组合物的一种或多种组分,作为组分的载体,作为去除残余物的助剂,作为组合物的粘度调节剂,以及作为稀释剂。优选地,清洁组合物中使用的水是去离子水(DIW)。水可以单独添加到组合物中,或者作为其他组分的水溶液的部分添加到组合物中,例如添加到组合物中的磷酸水溶液和/或含水氟离子源。以下段落中描述的水的范围包括来自任何来源的组合物中的所有水。
据信,对于大多数应用,组合物中水的重量百分比将存在于选自下列数字组的起点和终点的范围内:0.5、1、5、10、15、20、25、30、40、45、48、50、55、58、60、62、65、68、70、75、80、85、90和95。可用于组合物中的水的范围的实例包括例如约0.5%至约60重量%、或1%至约60重量%的水;或约0.5%至约40重量%、或约1%至约25重量%、或约1%至约20重量%、或约1%至约15重量%、或约5%至约20重量%、或约5%至约15重量%的水;或约40%至约70重量%、或约45%至约75重量%、或约40%至约60重量%、或约45%至约65重量%、或约50%至约70重量%、或约50%至约65重量%、或约40%至约75重量%、或约30%至约75重量%的水。本发明的其它优选实施方式可包括这样的水,其量可实现其它成分的期望重量百分比。
含磷无机酸
本发明的蚀刻组合物含有含磷无机酸或其盐。含磷无机酸主要用于蚀刻氮化钽(TaN)。含磷无机酸的实例包括,例如,磷酸(H3PO4),次磷酸(H3PO2),亚磷酸(H3PO3),连二磷酸(H4P2O6),偏磷酸(HPO3),过氧磷酸(H3PO5),及其盐。盐的实例包括磷酸的钠盐,例如NaH2PO4、Na2HPO4。含磷无机酸还包括其中,例如,通过消除水而将两个或更多个正磷酸分子通过缩合连接成较大分子的那些。因此,可以获得一系列多磷酸,其实例包括焦磷酸(H4P2O7),三聚磷酸(H5P3O10),四聚磷酸(H6P4O13),三偏磷酸(H3P3O9)和磷酸酐(P4O10)。
在一些实施方式中,使用磷酸。可以使用商业级磷酸。通常,可商购的磷酸可以作为80%至85%的水溶液获得。在优选的实施方式中,使用电子级磷酸溶液,其中这种电子级溶液通常具有低于100个颗粒/ml的颗粒计数,并且其中颗粒的尺寸小于或等于0.5微米,并且金属离子以低的每升百万分之几至十亿分之几的水平存在于酸中,例如1ppm或更低。除了可能添加氢氟酸之外,不将其他酸(例如硝酸或硫酸或其混合物)添加到本发明的组合物中。在一些实施方式中,可以加入HF作为氟离子源。
本发明的组合物基本上不含或不含其他氧化剂,例如过氧化物。因此,本发明的组合物基本上不含或不含过氧化物,例如过氧化氢、过硫酸盐(例如单过硫酸盐和二过硫酸盐)、过碳酸盐及其酸、及其盐、以及它们的混合物。
本发明的组合物还优选基本上不含或不含其它氧化剂,例如氧化的卤化物(例如碘酸盐、高碘酸盐及其酸、及其混合物等),过硼酸,过硼酸盐,过碳酸盐,过氧酸(例如过乙酸、过苯甲酸、其盐、其混合物等),高锰酸盐,铈化合物,铁氰化物(例如铁氰化钾),其混合物等。
在一些实施方式中,含磷无机酸或其盐(基于纯组合物)的重量百分比将在起点和端点选自下组数字的范围内:0.5,1,4,5,6,8,10,15,20,25,30,35,40,45,48,50,55,58,60,62,65,68,70,75和80。所述组合物中含磷无机酸的范围实例为约5%至约80%(重量),或约10%至约80%(重量),或约0.5%至约35%(重量),或约20%至约70%(重量),或约30%至约60%(重量),或约35%至约50%(重量),或约1%至约40%(重量),或约1%至约25%(重量),或约1%至约20%(重量),或约5%至约20%(重量),或约5%至约15%(重量)。在一些实施方式中,含磷无机酸的量将占所述组合物的约10%至约50%(重量)。
氟离子源
本公开的蚀刻组合物还包含一种或多种氟离子源。氟离子的作用主要是帮助去除TaN。提供根据本发明的氟离子源的典型化合物是氢氟酸、氟化铵、季铵氟化物如,例如氟硼酸盐、氟硼酸、四氟硼酸四丁基铵、六氟化铝、以及具有下式的脂族伯、仲或叔胺的氟化物盐:
R1NR2R3R4F,
其中R1、R2、R3和R4各自表示H或(C1-C4)烷基。通常,R1、R2、R3和R4基团中的碳原子总数为12个碳原子或更少。脂族伯、仲或叔胺的氟化物盐的实例例如为四甲基氟化铵、四乙基氟化铵、甲基三乙基氟化铵和四丁基氟化铵。
在选择氟离子源时,应考虑该源是否释放会对清洁的表面产生不利影响的离子。例如,在清洁半导体元件时,清洁组合物中钠或钙离子的存在可对元件表面产生不利影响。在优选的实施方式中,氟离子源是氟化铵。
据信,对于大多数应用,清洁组合物中用作氟离子源的化合物的量将包含约0.01至约8重量%或约0.01至约7重量%的40%氟化铵溶液,或其化学计量当量。优选地,该化合物包含约0.02至约8重量%、更优选约0.02至约6重量%、还更优选约1至约8重量%、最优选约0.025%至约5重量%的约40%氟化铵溶液。在一些实施方式中,组合物将包含约0.01至约8重量%或约0.01至约7重量%的氟离子源,其可由40%氟化铵溶液提供。优选地,该化合物包含约0.02至约6重量%的氟离子源,且最优选约0.025%至约5%或约0.04至约2.5重量%的氟离子源或约0.05%至约15重量%的40%氟化铵溶液,最优选约0.0625%至约12.5%或约0.1%至约6.25重量%的40%氟化铵溶液。然而,应理解,所使用的氟离子的量将通常取决于被清洁的特定衬底。例如,在某些清洁应用中,当清洁包含具有对氟蚀刻的高抗性的介电材料的衬底时,氟离子的量可以相对较高。相反,在其他应用中,例如,当清洁包含对氟蚀刻具有低耐受性的介电材料的衬底时,氟离子的量应该相对较低。
为了清楚起见,在仅添加氟离子源(纯)的基础上,清洁组合物中氟离子源的量可以包括起点和终点选自以下重量百分比列表的范围内的重量百分比:0.001,0.0016,0.002,0.0025,0.004,0.008,0.01,0.04,0.05,0.1,0.4,0.6,1,2,2.4,2.8,3,3.2,5,6,10,12,15和20。例如,组合物中氟离子源(纯)的量可以为约0.004至约3.2重量%或约0.004至约2.8重量%。组合物可包含约0.008至约3.2重量%,或约0.008至约2.4重量%,或约0.4至约3.2重量%,或约0.01%至约2重量%,或0.01%至约10重量%,或0.01重量%至约5重量%的氟离子源。在一些实施方式中,组合物包含约0.004至约3.2重量%的氟离子源。该组合物可包含的氟离子源为约0.001%至约2%或约0.0016至约1重量%的氟离子源或约0.002至约6重量%,或约0.0025%至约5%,或约0.04至约0.025重量%。在其他实施方式中,基于纯氟离子源的添加,组合物可包含约0.05至约20重量%,或约0.1至约15重量%,或约0.1至约20重量%,或约0.01至约20重量%,或约0.1至约10重量%或约0.1至约5重量%,或约0.6至约12重量%,或约1%至约20重量%,或约1至约15重量%,或约1至约10重量%的氟离子源。
水混溶性溶剂
本发明的蚀刻组合物包含水混溶性溶剂。可以使用的水混溶性有机溶剂的实例是乙二醇,丙二醇,丁基二甘醇,1,4-丁二醇,三丙二醇甲醚,丙二醇丙醚,二乙二醇正丁醚(例如,可以以商品名DowanolDB商购),己氧基丙胺,聚(氧乙烯)二胺,二甲基亚砜,四氢糠醇,甘油,醇类,亚砜类,或其混合物。优选的溶剂是醇、二醇或其混合物。最优选的溶剂是二醇,例如丙二醇。
在本发明的一些实施方式中,水混溶性有机溶剂可包含二醇醚。二醇醚的实例包括乙二醇单甲醚,乙二醇单乙醚,乙二醇单丁醚,乙二醇二甲醚,乙二醇二乙醚,二乙二醇单甲醚,二乙二醇单乙醚,二乙二醇单丙醚,二甘醇单异丙醚,二乙二醇单丁醚,二乙二醇单异丁醚,二乙二醇单苄基醚,二乙二醇二甲醚,二乙二醇二乙醚,三乙二醇单甲醚,三乙二醇二甲醚,聚乙二醇单甲醚,二乙二醇甲乙醚,三甘醇乙二醇单甲醚乙酸酯,乙二醇单乙醚乙酸酯,丙二醇甲醚乙酸酯,丙二醇单甲醚,丙二醇二甲醚,丙二醇单丁醚,丙二醇单丙醚,二丙二醇单甲醚,二丙二醇单丙醚,二丙二醇单异丙醚,二丙二醇单丁醚(dipropylenemonobutyl ether),二丙二醇二异丙醚,三丙二醇单甲醚,1-甲氧基-2-丁醇,2-甲氧基-1-丁醇,2-甲氧基-2-甲基丁醇,1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。
据信,对于大多数应用,组合物中水混溶性有机溶剂的量可以在具有选自以下重量百分比列表的起点和终点的范围内:0.5,1,5,7,12,15,20,30,35,40,50,59.5,65,68和70。这种溶剂范围的实例包括基于组合物的约0.5%至约59.5重量%;或约1%至约50重量%;或约1%至约40重量%;或约0.5%至约30重量%;或约1%至约30重量%;或约5%至约30重量%;或约5%至约15重量%;或约7%至约12重量%。
任选成分
本发明的蚀刻组合物还可包含一种或多种下列添加剂:螯合剂、表面活性剂、化学改性剂、染料、杀生物剂和其他添加剂。添加剂可以添加到它们不会对组合物的性能产生不利影响的程度。
可用于蚀刻组合物的另一种任选成分是金属螯合剂;它可以起到增加组合物将保持金属在溶液中和增强金属残余物溶解的作用的能力。可用于此目的的螯合剂的典型实例是下列有机酸及其异构体和盐:乙二胺四乙酸(EDTA),丁二胺四乙酸,(1,2-亚环己基二胺)四乙酸(CyDTA),二亚乙基三胺五乙酸(DETPA),乙二胺四丙酸,(羟乙基)乙二胺三乙酸(HEDTA),N,N,N',N'-乙二胺四(亚甲基膦)酸(EDTMP),三亚乙基四胺六乙酸(TTHA),1,3-二氨基-2-羟基丙烷-N,N,N',N'-四乙酸(DHPTA),甲基亚氨基二乙酸,丙二胺四乙酸,硝基三乙酸(NTA),柠檬酸,酒石酸,葡萄糖酸,糖酸,甘油酸,草酸,邻苯二甲酸,马来酸,扁桃酸,丙二酸,乳酸,水杨酸,没食子酸丙酯,连苯三酚,8-羟基喹啉和半胱氨酸。优选的螯合剂是氨基羧酸,如EDTA、CyDTA和氨基膦酸,如EDTMP。
据信,螯合剂(如果存在)在组合物中的量为组合物的约0.1重量%至约10重量%,优选约0.5重量%至约5重量%。
在一些实施方式中,本发明的组合物将不含或基本上不含添加到组合物中的任何或所有上面列出的螯合剂。
其他通常已知的组分如染料、表面活性剂、杀生物剂等可以常规量包含在清洁组合物中,例如,高达组合物的总共约5重量%的量。
在一些实施方式中,本发明的组合物将不含或基本上不含染料、表面活性剂和/或杀生物剂中的任一者或全部。
在一些实施方式中,本文公开的蚀刻溶液组合物被配制成基本上不含或不含无机碱和/或季铵氢氧化物,例如,所述组合物可基本上不含或不含以下的一种或多种:四甲基氢氧化铵,四乙基氢氧化铵,甲基三乙基氢氧化铵和/或四丁基氢氧化铵。在一些实施方式中,组合物可基本上不含或不含下列中的一种或多种:氢氧化物,金属氢氧化物,例如KOH或LiOH或NaOH。在其他实施方式中,组合物可以基本上不含或不含除一种或多种含氟化合物之外的含卤素化合物,例如其可以基本上不含或不含以下一种或多种:含溴化合物、含氯化合物、或含碘化合物。在其他实施方式中,组合物可以基本上不含或不含磺酸和/或硫酸和/或硝酸和/或盐酸。在其他实施方式中,组合物可以基本上不含或不含硫酸盐和/或硝酸盐和/或亚硫酸盐和/或亚硝酸盐。在其他实施方式中,组合物可以基本上不含或不含:氢氧化铵和/或乙基二胺。在其他实施方式中,组合物可以基本上不含或不含:含钠化合物和/或含钙化合物和/或含锰化合物或含镁化合物和/或含铬化合物和/或含硫化合物和/或含钼化合物。在其他实施方式中,组合物可以基本上不含或不含:过氧化合物,即包含至少一个过氧基团(-O-O-)的化合物,例如过氧化物和/或过硫酸盐、和/或过碳酸盐、和/或其酸、和/或其盐、和/或其混合物。在其他实施方式中,组合物可以不含或基本上不含以下一种或多种(单独或与本段中任何其他组分组合):碘酸盐,高碘酸盐,过硼酸,过硼酸盐,过氧酸(例如过氧乙酸),过氧苯甲酸,高锰酸盐,铈化合物,铁氰化物(例如铁氰化钾),或其盐,或其混合物等。本发明的蚀刻溶液组合物通常通过在室温下在容器中将组分混合在一起直至所有固体溶解在水基介质中来制备。
方法
在另一方面,提供了一种在包含氮化钽和氮化钛的微电子器件中相对于氮化钛而选择性地提高氮化钽的蚀刻速率的方法,所述方法是通过在包含磷酸和水混溶性溶剂、基本上由磷酸和水混溶性溶剂组成、或由磷酸和水混溶性溶剂组成的组合物中蚀刻复合微电子器件而实现。所述方法包括以下步骤:使包含氮化钽与氮化钛的复合微电子(半导体)器件与包含磷酸和水混溶性溶剂、基本上由磷酸和水混溶性溶剂组成、或由磷酸和水混溶性溶剂组成的组合物接触;和在所述氮化钽被至少部分地去除之后冲洗所述复合半导体器件。该方法中还可包括另外的干燥步骤。“至少部分地去除”是指通过使用本发明的组合物去除至少50%的材料,优选至少70%去除。最优选地,80%去除。
接触步骤可以通过任何合适的方式进行,例如浸渍、喷雾或通过单晶片工艺。接触步骤期间组合物的温度优选为约25℃至约150℃或约25℃至约100℃,更优选为约30℃至约60℃。接触时间可以是30秒至60分钟或1至60分钟或1至30分钟。可以根据待蚀刻的一个或多个TaN层的厚度和/或存在于半导体器件上待保留的一个或多个TiN层来调整处理时间。
在优选的实施方式中,对于本发明的组合物观察到的氮化钽相对于氮化钛的蚀刻选择性为至少约2或至少约5。优选地,对于本发明的组合物观察到的蚀刻选择性是约5至约125或更多,更优选约5至约80或更多,或至少约9,或约9至125或更多,或约20至125或更多或者30至125或更多。
在接触步骤之后是任选的冲洗步骤。冲洗步骤可以通过任何合适的方式进行,例如,通过浸渍或喷雾技术用去离子水冲洗衬底。在优选的实施方式中,冲洗步骤可以使用去离子水和有机溶剂(例如异丙醇)的混合物进行。
在接触步骤和任选的冲洗步骤之后是任选的干燥步骤,其通过任何合适的方式进行,例如异丙醇(IPA)蒸气干燥、加热或通过向心力。
通过下面讨论的说明性实施例更充分地示出了特征和优点。
实施例
制备清洁组合物的一般程序
通过用1”特氟隆涂覆的搅拌棒将组分在250mL烧杯中混合来制备作为本实施例主题的所有组合物。通常,添加到烧杯中的第一材料是去离子(DI)水。随后通常加入磷酸,然后加入水混溶性溶剂和氟离子源。
衬底的组成
试样是具有TaN的硅晶片和具有TiN的硅晶片。
处理条件
使用100g蚀刻组合物在250ml烧杯中进行蚀刻测试,其中将1/2”圆形特氟隆搅拌棒设定在400rpm。在热板上将蚀刻组合物加热至约40℃的温度。在搅拌下将试样浸入组合物中约20分钟。
对于TaN晶片,蚀刻速率从35℃至45℃测量2分钟,对于TiN晶片测量10分钟。通过处理之前和之后的厚度差异除以浸渍时间来计算蚀刻速率。
然后将节段在DI水浴或喷雾中冲洗3分钟,随后使用过滤的氮气干燥。根据蚀刻前后的厚度变化估算氮化钽和氮化钛的蚀刻速率,并通过CDE 172 4点resmap来测量。对于氮化钽,典型的起始层厚度为对于氮化钛,典型的起始层厚度为
比较例
表1和2中的组合物显示,在高碱性环境制剂中可以通过H2O2蚀刻TaN。然而,其对于蚀刻TiN膜更具侵蚀性。在NH4OH/H2O2溶液中,TaN相对于TiN的选择性小于1。还测试了BOE(HF/NH4F混合物),但其不像NH4OH/H2O2平台那样具有侵蚀性。
表1:NH4OH/H2O2平台中的蚀刻速率
248E | 248J | |
NH<sub>4</sub>OH(29%) | 10 | 0 |
H<sub>2</sub>O<sub>2</sub>(30%) | 50 | 50 |
DIW | 40 | 50 |
TaN e/r@60C | 4.04 | 0.12 |
TiN e/r@60C | 9.25 | 9.85 |
TaN/TiN选择性 | 0.44 | 0.01 |
表2:BOE(HF/NH4F)平台中的蚀刻速率
248M | 248N | |
BOE | 100 | 50 |
DIW | 50 | |
25℃下的TaN e/r | 1.14 | 1.43 |
25℃下的TiN e/r | 1.9 | 1.93 |
TaN/TiN 选择性 | 0.60 | 0.74 |
实施例1
表3中评价的组合物表明,在氟化铵的存在下,可以相对于TiN而选择性地蚀刻TaN。
表3:氟化铵在蚀刻TaN中的作用
250E | 250G | 250I | 250J | 250K | 250L | |
DIW | 30 | 45 | 50 | 55 | 57.5 | 60 |
NH<sub>4</sub>F(40%) | 30 | 15 | 10 | 5 | 2.5 | 0 |
甘油 | 30 | 30 | 30 | 30 | 30 | 30 |
H<sub>3</sub>PO<sub>4</sub>(85%) | 10 | 10 | 10 | 10 | 10 | 10 |
40℃下的TaN e/r | 4.88 | 5.52 | 4.97 | 4.92 | 1.38 | 0.14 |
40℃下的TiN e/r | 0.15 | 0.17 | 0.17 | 0.16 | 0.17 | 0.16 |
TaN/TiN选择性 | 32.5 | 32.5 | 29.2 | 30.8 | 8.1 | 0.9 |
实施例2
表4中评价的组合物表明,H3PO4可有效地蚀刻TaN。
表4:酸在蚀刻TaN中的作用
250O | 250S | 250T | 250U | 250V | |
DIW | 85 | 90 | 93 | 93 | 93 |
NH<sub>4</sub>F(40%) | 5 | 5 | 5 | 5 | 5 |
H<sub>3</sub>PO<sub>4</sub>(85%) | 10 | 5 | 0 | 0 | 0 |
草酸 | 0 | 0 | 2 | ||
丙二酸 | 2 | ||||
柠檬酸 | 2 | ||||
40℃下的TaN e/r | 4.65 | 1.44 | 1.67 | 0.07 | 0.76 |
40℃下的TiN e/r | 0.17 | 0.16 | 0.18 | 0.17 | 0.17 |
TaN/TiN选择性 | 27.4 | 9.0 | 9.3 | 0.4 | 4.5 |
实施例3
表5中评价的组合物表明,甘油表现出提高TaN相对于TiN的蚀刻选择性的良好潜力。
表5:不同溶剂对蚀刻速率的影响
实施例4
基于以上研究,将优化的制剂(257N)(表6)施加在TaN/TiN双层晶片上。进行XPS以检查顶部的TaN是否被完全除去,并且使用TEM横截面来检查底部的TiN膜是否被损坏。
表6
257N | |
DIW | 52.5 |
NH4F(40%) | 7.5 |
H3PO4(85%) | 15 |
PG | 25 |
40℃下的TaNe/r | 6.5 |
40℃下的TiNe/r | 0.17 |
TaN/TiN 选择性 | 38.2 |
参见图1,XPS信号表明大部分TaN层通过制剂257N在40℃/3分钟的条件下被去除。
前面的描述主要用于说明的目的。尽管已经参照本发明的示例性实施方式示出和描述了本发明,但是本领域技术人员应该理解,可以在其中进行前述和其形式和细节的各种其他改变、省略和添加而不背离本发明的精神和范围。
Claims (17)
1.一种适合于从微电子器件中相对于氮化钛而选择性地去除氮化钽的蚀刻溶液,所述蚀刻溶液包含:
水;
含磷无机酸;
氟离子源;和
水混溶性有机溶剂。
2.根据权利要求1所述的蚀刻组合物,其中所述水混溶性溶剂选自乙二醇、丙二醇、丁基二甘醇、1,4-丁二醇、三丙二醇甲醚、丙二醇丙醚、二乙二醇正丁醚、己氧基丙胺、聚(氧乙烯)二胺、二甲基亚砜、四氢糠醇、甘油、醇类、亚砜类或其混合物。
3.根据权利要求1或2所述的蚀刻组合物,其中所述水混溶性溶剂选自丁基二甘醇、甘油或丙二醇或其混合物。
4.根据权利要求1-3任一项所述的蚀刻组合物,其中所述氟离子源选自氢氟酸,氟化铵,氟化氢铵,季铵氟化物如,例如氟硼酸盐,氟硼酸,四氟硼酸四丁基铵,六氟化铝,以及具有下式的脂族伯、仲或叔胺的氟化物盐:
R1NR2R3R4F,
其中R1、R2、R3和R4各自表示H或(C1-C4)烷基,及其混合物。
5.根据权利要求1-4任一项所述的蚀刻组合物,其中所述氟离子源选自氟化铵、氟化氢铵、四甲基氟化铵、四乙基氟化铵、甲基三乙基氟化铵和四丁基氟化铵,及其混合物。
6.根据权利要求1-5任一项所述的蚀刻组合物,其中所述氟离子源包含氟化铵。
7.根据权利要求1-6任一项所述的蚀刻组合物,其中所述含磷无机酸选自磷酸(H3PO4),次磷酸(H3PO2),亚磷酸(H3PO3),连二磷酸(H4P2O6),偏磷酸(HPO3),过氧磷酸(H3PO5),焦磷酸(H4P2O7),三聚磷酸(H5P3O10),四聚磷酸(H6P4O13),三偏磷酸(H3P3O9)和磷酸酐(P4O10)及其盐和它们的混合物。
8.根据权利要求1-7任一项所述的蚀刻组合物,其中所述含磷无机酸包含磷酸(H3PO4)。
9.根据权利要求1-8任一项所述的蚀刻组合物,其中所述组合物基本上不含氧化剂。
10.根据权利要求1-9任一项所述的蚀刻组合物,其中所述组合物包含:
约0.5重量%至约50重量%的所述含磷无机酸(纯);
约0.01重量%至约20重量%的氟离子源(纯);和
约1重量%至约50重量%的水混溶性有机溶剂。
11.根据权利要求1-10任一项所述的蚀刻组合物,其中所述组合物包含:
约0.5重量%至约35重量%的所述含磷无机酸(纯);
约0.01重量%至约10重量%的氟离子源(纯);和
约1重量%至约40重量%的水混溶性有机溶剂。
12.根据权利要求1-11任一项所述的蚀刻组合物,其中所述组合物包含:
约1重量%至约25重量%的所述含磷无机酸(纯);
约0.1重量%至约10重量%的氟离子源(纯);和
约1重量%至约30重量%的水混溶性有机溶剂。
13.根据权利要求1-12任一项所述的蚀刻组合物,其中所述组合物提供的氮化钽相对于氮化钛的蚀刻选择性至少为5。
14.一种在包含氮化钽和氮化钛的微电子器件上相对于氮化钛选择性地提高氮化钽的蚀刻速率的方法,所述方法包括以下步骤:
使所述包含氮化钽和氮化钛的微电子器件与根据权利要求1-13任一项的蚀刻组合物接触;和
在所述氮化钽被至少部分地去除之后冲洗所述微电子器件,其中氮化钽相对于氮化钛的蚀刻的选择性大于3。
15.根据权利要求14所述的方法,所述方法还包括干燥所述微电子器件的步骤。
16.根据权利要求14或15所述的方法,其中氮化钽相对于氮化钛的蚀刻选择性为约9至约125。
17.根据权利要求14-16任一项所述的方法,其中所述接触步骤在约25℃至约100℃的温度下进行。
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