CN1609156B - 用于抛光半导体层的组合物 - Google Patents
用于抛光半导体层的组合物 Download PDFInfo
- Publication number
- CN1609156B CN1609156B CN2004100558419A CN200410055841A CN1609156B CN 1609156 B CN1609156 B CN 1609156B CN 2004100558419 A CN2004100558419 A CN 2004100558419A CN 200410055841 A CN200410055841 A CN 200410055841A CN 1609156 B CN1609156 B CN 1609156B
- Authority
- CN
- China
- Prior art keywords
- layer
- teos
- polishing
- removal
- polishing composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000005498 polishing Methods 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000004065 semiconductor Substances 0.000 title description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 51
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 40
- 230000000903 blocking effect Effects 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 63
- 229910052751 metal Inorganic materials 0.000 abstract description 31
- 239000002184 metal Substances 0.000 abstract description 31
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- 239000003112 inhibitor Substances 0.000 abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 8
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
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- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 16
- -1 sulfate radical Chemical class 0.000 description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 16
- 239000000654 additive Substances 0.000 description 14
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- 235000010333 potassium nitrate Nutrition 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
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- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
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- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 6
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 6
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 150000003839 salts Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
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- 239000011572 manganese Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- QHOKENWFMZXSEU-UHFFFAOYSA-N tetrabutylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC QHOKENWFMZXSEU-UHFFFAOYSA-N 0.000 description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000003107 substituted aryl group Chemical group 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- DDEDTRQKFDAWHH-UHFFFAOYSA-N 4-[(6-iodo-1,3-benzothiazol-2-yl)diazenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=NC2=CC=C(I)C=C2S1 DDEDTRQKFDAWHH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
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- 238000007689 inspection Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
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- 239000002563 ionic surfactant Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229940050176 methyl chloride Drugs 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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Abstract
包含用于限制互连金属去除的腐蚀抑制剂且具有酸性pH的水性抛光组合物。该组合物包含与构成的包含有机物的铵盐,R1,R2,R3和R4是原子团,R1具有2至15个碳原子的碳链长度。该包含有机物的铵盐具有一定浓度,该浓度可加速TEOS的去除而减少至少一种选自SiC,SiCN,Si3N4和SiCO的覆层的去除。
Description
技术领域
本公开涉及用于改变半导体器件中含氧化硅层的去除速率的抛光组合物。本公开同时涉及用于从底层如SiC,SiCN,Si3N4或SiCO上去除含氧化硅层的化学机械平坦化(CMP)工艺。
背景技术
芯片制造商使用多重化学-机械-平坦化(CMP)步骤来平坦化晶片以促进平坦衬底表面的生产。这些平坦表面有利于多层集成电路的生产,且不会产生将电介质涂覆到不平坦衬底上时形成的有害畸变。
典型地以两步程序进行该CMP工艺以便改善抛光性能。首先,该抛光工艺使用特别设计的“第一步”浆料快速去除互连金属,例如铜。在这个最初的铜去除步骤之后,“第二步”浆料去除阻挡层。典型地,该第二步浆料具有选择性,可除去阻挡层而不会使该互连金属“凹陷”(dishing)从而对互连结构的物理结构或电性能产生有害影响。阻挡层的去除速率与金属互连或介电层的去除速率的比值被称为选择系数。对本说明书而言,去除速率是指每单位时间厚度的变化,例如埃每分钟。
去除阻挡层之后,该浆料可典型去除底层,例如含氧化硅的材料。对于本发明,含氧化硅材料包括由硅烷衍生的材料例如原硅酸四乙酯(TEOS)和除了SiCO或SiOC的其它用于生产半导体的含氧化硅涂层。遗憾的是,以快的去除速率去除含氧化硅材料的浆料倾向于以无法接受的去除速率同时除去下面的掩模(mask),封盖层(cap),抗反射覆层和电介质,特别是低k和超低k电介质。这些底层的非控制去除会对集成电路的最终性能产生有害影响。
CMP抛光组合物包含用于铜去除配方的醇胺成份。例如,Steckenrider等人在美国公开20020032987中公开了具有9到10.5的pH的金属抛光组合物,该组合物含有醇胺。这种组合物具有大于100的多晶硅相对绝缘层的选择性。然而,这些抛光组合物使用了具有大于或等于400纳米尺寸的研磨颗粒,而且对于含氧化硅的层例如TEOS掩模层,没有显示出所需的选择性。
在一些低k电介质和超低k集成方案(scheme)中,在电介质之上沉积封盖材料以保护该电介质不受机械损伤。然后在该封盖层之上的掩模层如TEOS,通过用图案腐蚀工艺除去该掩模层从而在该集成电路内限定电介质或互连金属的区域。腐蚀之后,用阻挡层覆盖该衬底然后用金属层,例如铜,填充该通道或过孔。对于有效的CMP,这些半导体集成方案典型需要掩模层如TEOS掩模层的选择性去除,并具有低水平的金属互连凹陷和最小限度的底部封盖层去除。然而对于一些集成方案,同时除去较低的封盖层并在低k电介质上停止是有利的。
因为含氧化硅的层如TEOS相比低k和超低k材料具有较高的介电常数,所以应使这些TEOS层尽可能的薄以便维持该晶片低的有效介电常数。然而因为较厚的TEOS层可改善CMP集成的工艺控制,所选的最终厚度显示了这两个竞争作用的折中。由这种折中产生的“厚”TEOS层需要具有有效掩模层去除步骤的抛光组合物,该步骤具有受控的互连金属去除速率。
总之,这些半导体集成方案需要含氧化硅层的选择性去除,该去除具有有效的去除速率而且可在下面的封盖层或介电层上停止。鉴于这些考虑,存在提供可容许含氧化硅层的受控去除的抛光组合物的需求。另外,存在去除含氧化硅层如TEOS掩模层,且具有减少的缺陷的持续需求。
此外,由于半导体制造商依赖于不同的集成方案和低k/超低k材料,半导体用户对该CMP浆料有不同的要求。这些不同的集成方案致使配置通用的抛光溶液极为困难。因此,调节含氧化硅层,封盖层,以及金属互连例如铜的去除速率以满足多种集成方案也是有效的。
发明内容
本发明提供了一种水性抛光组合物,该组合物包含用于限制互连金属的去除的腐蚀抑制剂;具有酸性pH;且包含与
构成的包含有机物的铵盐,R1,R2,R3和R4是原子团,R1具有2至15个碳原子的碳链长度且该包含有机物的铵盐具有一定浓度,在使用至少一种小于21.7kPa的抛光压力的情况下,该浓度能加速TEOS的去除并能减少选自SiC,SiCN,Si3N4和SiCO的至少一种覆层的去除。
本发明同时包括用于从半导体衬底上除去一层的方法,该方法包括:将水性抛光组合物涂覆到该半导体衬底上,该水性抛光组合物包含与
构成的包含有机物的铵盐,R1,R2,R3和R4是原子团,R1具有2至15个碳原子的碳链长度以便加速含氧化硅层的去除;和用抛光垫对含氧化硅层进行抛光,以便从该半导体衬底上除去该含氧化硅层。
附图说明
图1是TEOS的去除速率与抛光组合物中硝酸钾和铵盐的添加浓度的关系的图解表示。
图2是碳氮化硅(SiCN)的去除速率与抛光组合物中硝酸钾和铵盐的摩尔添加浓度的关系的图解表示。
图3是初始抛光组合物的ζ电位与初始抛光组合物中硝酸钾或铵盐浓度的关系的图解表示。
图4是TEOS的去除速率与初始抛光组合物中铵盐的摩尔添加浓度的关系的图解表示。
图5是氮化钽(TaN)的去除速率与初始抛光组合物中铵盐的摩尔添加浓度的关系的图解表示。
图6是说明碱性常规浆料和含铵盐的酸性浆料之间的薄铜板晶片缺陷的比较的图示。
具体实施方式
已发现铵盐有利于在酸性pH水平上受控的含氧化硅层如TEOS层的去除速率,从而容许控制该含氧化硅材料的去除速率。该铵盐是与化合物形成的有机铵盐,以包括下列结构:
R1,R2,R3和R4是可以相同或者不同的基团。该组合物在酸性pH下起作用,这时该铵化合物发生离子化。阴离子的实例包括,硝酸根,硫酸根,卤离子(例如溴离子,氯离子,氟离子和碘离子),柠檬酸根,磷酸根,草酸根,苹果酸根,葡萄糖酸根,氢氧根,乙酸根,硼酸根,乳酸根,硫氰酸根,氰酸根,磺酸根,硅酸根,全卤化物离子(例如过溴酸根,高氯酸根和高碘酸根),铬酸根,和包含至少一种前述阴离子的混合物。可以将该盐直接加入该组合物或者在原位形成该盐。例如,将氢氧化四甲铵加入到pH为2.5的硝酸溶液中可形成硝酸四甲铵。
优选的铵盐组合是氢氧化四丁铵与氢氟酸反应形成的。这种组合在低pH水平发生反应从而形成氟化四丁铵盐。虽然不清楚确切的机制(该氟化物盐离解从而在溶液中提供氟离子),但溶液中包含有机氟化铵盐可进一步加快TEOS的去除速率。
R1是具有2到15个碳原子的碳链长度的有机物。更优选地,R1具有2到10的碳链长度。最优选地,R1具有2到5个碳原子的碳链长度。该有机物R1可以是取代或非取代芳基,烷基,芳烷基,或烷芳基。
优选地,R2,R3和R4是有机化合物,例如取代或非取代芳基,烷基,芳烷基,或烷芳基;或氢。如果R2,R3或R4是有机化合物,这时该有机化合物优选具有2至15个碳原子的碳链长度;更优选地,该化合物具有2至10个碳原子的碳链长度;且最优选地该化合物具有2到5个碳原子的碳链长度。
用于构成铵盐的适合化合物包括四乙铵,四丁铵,苄基三丁铵,苄基三甲铵,苄基三乙铵,二烯丙基二甲铵,甲基丙烯酸二乙基氨基乙酯,甲基丙烯酸二甲基氨基乙酯,甲基丙烯酰氧基乙基三甲铵,3-(甲基丙烯酰胺基)丙基三甲铵,三亚乙基四胺,四甲胍,己胺和包含至少一种前述铵盐的混合物。具体的铵盐包括硝酸四乙铵,氟化四丁铵,硝酸四乙铵,氟化四乙胺,氯化苄基三丁铵,氯化苄基三甲铵,氯化苄基三乙铵,氯化二烯丙基二甲铵,氯化二烯丙基二乙胺,甲基丙烯酸二乙基氨基乙酯,甲基丙烯酸二甲基氨基乙酯,硫酸甲基丙烯酰氧基乙基三甲铵,氯化甲基丙烯酰氧基乙基三甲铵,氯化3-(甲基丙烯酰胺基)丙基三甲铵,三亚乙基四胺,四甲胍,己胺和包含上述至少一种的混合物。优选的铵盐是四乙铵盐,四丁铵盐,苄基三丁铵盐,苄基三甲铵盐和苄基三乙铵盐。
该铵盐存在的量是0.001重量百分比(wt%)至3wt%。对于本发明,所有的浓度以基于该抛光组合物的总重量的重量百分比表示,除非另外明确注明。优选地,该铵盐以大于或等于0.02wt%的量存在,且优选大于或等于0.05wt%。此外该范围内理想的量是小于或等于2wt%,优选小于或等于1wt%,且更优选小于或等于0.5wt%。
该抛光组合物可以选择性地包含最高25wt%的研磨剂以促进氧化硅的去除或阻挡层和氧化硅一起的去除——这取决于该集成方案,该抛光组合物可用来去除掩模层,或者首先去除阻挡层然后去除含氧化硅层。该抛光组合物可选包含用于“机械”去除阻挡层的研磨剂。该研磨剂优选是胶态研磨剂。研磨剂的实例包括无机氧化物,金属硼化物,金属碳化物,金属氮化物,聚合物颗粒和包含前述至少一种的混合物。适合的无机氧化物包括,例如二氧化硅(SiO2),氧化铝(Al2O3),氧化锆(ZrO2),二氧化铈(CeO2),氧化锰(MnO2),或包含至少一种前述氧化物的混合物。如果需要,也可以使用这些无机氧化物的改良形式,例如聚合物包覆的无机氧化物颗粒和无机物包覆的颗粒。适合的金属碳化物,硼化物和氮化物包括,例如碳化硅,氮化硅,碳氮化硅(SiCN),碳化硼,碳化钨,碳化锆,硼化铝,碳化钽,碳化钛,或者包含至少一种前述金属碳化物、硼化物和氮化物的混合物。如果需要也可以使用金刚石作为研磨剂。可选的研磨剂还包括聚合物颗粒和包覆的聚合物颗粒。优选的研磨剂是二氧化硅。
希望以基于该抛光组合物的全部重量的0.05wt%至15wt%的量使用该研磨剂。在这个范围之内,使该研磨剂的存在量大于或等于0.1wt%是理想的,且优选大于或等于0.5wt%。在这个范围之内,同时希望该量小于或等于10wt%,且优选小于或等于5wt%。
该研磨剂具有小于或等于150纳米(nm)的平均颗粒尺寸,以防止过度的金属凹陷和电介质腐蚀。就本说明书而言,颗粒尺寸是指该研磨剂的平均颗粒尺寸。使用具有小于或等于100nm的平均颗粒尺寸的胶态研磨剂是理想的,优选小于或等于50nm,且更优选小于或等于40nm。使用具有小于或等于40nm的平均颗粒尺寸的胶态二氧化硅有利于产生最少的电介质腐蚀和金属凹陷。将该胶态研磨剂的尺寸减小到小于或等于40nm,趋于提高该抛光组合物的选择性;但同时趋于减小阻挡层的去除速率。另外,优选的胶态研磨剂可以包含添加剂,例如分散剂,表面活性剂和缓冲剂,以提高在酸性pH范围内该胶态研磨剂的稳定性。一种这样的胶态研磨剂是购自法国Puteaux ClariantS.A.的胶态二氧化硅。该化学机械平坦化组合物还可选择性包含配位剂,螯合剂,pH缓冲剂,杀菌剂和消泡剂。
如果该抛光组合物不包含研磨剂,这时垫的选择和调整对于化学机械平坦化(CMP)工艺变得更为重要。例如,对于一些无研磨剂组合物,固定的研磨垫可提高抛光性能。
可选地,氧化剂的使用有利于优化阻挡层,例如钽,氮化钽,钛和氮化钛的去除速率。适合的氧化剂包括,例如过氧化氢,单过硫酸盐,碘酸盐,过邻苯二甲酸镁,过乙酸和其它过酸,过硫酸盐,溴酸盐,高碘酸盐,硝酸盐,铁盐,铈盐,锰(Mn)(III),Mn(IV)和Mn(VI)盐,银盐,铜盐,铬盐,钴盐,卤素,次氯酸盐,或包含至少一种前述氧化剂的混合物。优选的氧化剂是过氧化氢。应注意的是典型就在使用之前将该氧化剂加入该抛光组合物中,且在这种情形下将该氧化剂包含于单独的包装内。
0到10wt%用量的氧化剂是理想的。在这个范围之内,大于或等于0.1wt%量的氧化剂是理想的。此外在这个范围内小于或等于5wt%量的氧化剂是理想的。最优选地,该组合物包含0.1至5wt%的氧化剂。调整氧化剂如过氧化物的量还可以控制金属互连的去除速率。例如,提高过氧化物的浓度可以提高铜的去除速率。然而,氧化剂的过度增加会对抛光速率产生有害的影响。
该抛光组合物具有可产生高的阻挡层去除速率的酸性pH。适合用于该互连的金属包括,例如铜,铜合金,金,金合金,镍,镍合金,铂族金属,铂族金属合金,银,银合金,钨,钨合金和包含至少一种前述金属的混合物。优选的互连金属是铜。在使用例如过氧化氢的氧化剂的酸性抛光组合物和浆料中,主要由于铜的氧化,铜的去除速率和静态腐蚀速率都较高。为了减小互连金属的去除速率,该抛光组合物使用了腐蚀抑制剂。该腐蚀抑制剂的作用是减少互连金属的去除。通过减少互联金属的凹陷从而有助于改善抛光性能。
该抑制剂的存在量典型为最高6wt%——该抑制剂可以是对于该互联金属的单一抑制剂或其抑制剂的混合物。在这个范围之内,含有大于或等于0.0025wt%量的抑制剂是理想的,优选大于或等于0.25wt%。在这个范围之内小于或等于4wt%的量也是理想的,且优选小于或等于1wt%。优选的腐蚀抑制剂是苯并三唑(BTA)。在一个实施方案中,该抛光组合物可以包含相对大量的BTA抑制剂以减小该互连的去除速率。在0.25wt%以上的BTA浓度中,可以不必添加辅助的腐蚀抑制剂。优选的BTA浓度是0.0025至2wt%。
另外的腐蚀抑制剂包括表面活性剂,例如阴离子表面活性剂,非离子表面活性剂,两性表面活性剂和聚合物,或有机化合物,例如唑系(azoles)。适合的阴离子表面活性剂包括例如含有例如磺酸根,硫酸根,羧酸根,磷酸根,或这些官能团的衍生物的官能团的表面活性剂,或包含至少一种前述表面活性剂的混合物。优选的阴离子表面活性剂是十二烷基苯磺酸钠。适合的非离子表面活性剂包括,例如硅基化合物,氟基化合物,酯,环氧乙烷,醇,乙氧基化物,醚,配糖体,或这些化合物的衍生物,或包含至少一种前述非离子表面活性剂的混合物。适合的两性表面活性剂或聚合物包括,例如聚羧酸酯和它们的衍生物,聚丙烯酰胺和它们的衍生物,纤维素,聚乙烯醇和它们的衍生物,和聚乙烯吡咯烷酮和它们的衍生物。可以用作抑制剂或用于抑制剂混合物中的适合的唑系包括,例如甲苯基三唑(TTA),咪唑和它们的混合物。最优选的辅助腐蚀抑制剂是甲苯基三唑。
该抛光组合物还包含无机或有机pH调节剂以便将该抛光组合物的pH降至小于或等于5的酸性pH。适合的无机pH调节剂包括,例如硝酸,硫酸,盐酸,磷酸或包含至少一种前述无机pH调节剂的混合物。优选的pH调节剂是硝酸(HNO3)。
该抛光组合物在酸性pH下起作用。该抛光组合物的pH优选小于或等于5。在这个范围之内大于或等于1,优选大于或等于1.5的pH是理想的。在这个范围之内小于或等于4,优选小于或等于3的pH同样是理想的。对于该抛光组合物最优选的pH是2至3。
在小于3的pH下,该抛光组合物能够提供高的阻挡层金属去除速率,即使该抛光组合物中只包含相对低的重量百分比的研磨剂。通过减少研磨剂所引起的不希望的缺陷例如划痕,这种低的研磨剂浓度可以提高CMP工艺的抛光性能。例如小至约10nm的颗粒尺寸仍可提供可接受的阻挡层去除速率。通过使用具有相对小的颗粒尺寸的研磨剂并以低的研磨剂浓度配置该抛光组合物,可进一步减少抛光缺陷。
可选地,该抛光组合物可以包含螯合剂或配位剂,以便相对于阻挡层金属的去除速率调节铜的去除速率。该螯合剂可以通过与铜形成螯合金属配合物从而提高铜的去除速率。适合的螯合剂包括,例如羧酸,氨基羧酸和它们的衍生物,或包含至少一种前述螯合剂的混合物。优选地,存在于该抛光组合物中的螯合剂的量是小于或等于2wt%,基于该抛光组合物的总重量。可选地,该抛光组合物还可以包含缓冲剂例如各种有机酸和无机酸,和氨基酸或它们的盐,且具有1.5到小于3范围的以pH表示的pKa。可选地,该抛光组合物可进一步包含消泡剂,例如非离子表面活性剂,包括酯,环氧乙烷,醇,乙氧基化物,硅化合物,氟化合物,醚,配糖体和它们的衍生物。该消泡剂还可以是两性表面活性剂。
该抛光组合物可使该CMP设备在2.5至15千帕(kPa)的低压下工作。在这个范围内,优选3至12kPa的压力。该低CMP垫压可通过减少划痕和其它不希望的抛光缺陷来改善抛光性能,并最大程度上减小对脆性材料的损伤。例如,当暴露于高应力时,低介电常数的材料会破裂和剥离。此外,由该抛光组合物获得的高阻挡层金属去除速率能够在使用低的研磨剂浓度和小的研磨剂颗粒尺寸时,提供有效的阻挡层金属去除速率和含氧化硅层如TEOS去除速率。在一个示例性的实施方案中,可以对该抛光组合物进行调节或调整以便有利地获得高的阻挡层去除速率而不对该含氧化硅层产生任何破坏。也可以对其进行有利地调整以便去除该含氧化硅层而不对该低k或超低k介电层产生任何损伤。
对于小于21.7kPa(3psi)的至少一种抛光压力,该组合物可加速TEOS的去除并减少至少一种选自SiC,SiCN,Si3N4和SiCO的覆层的去除,该抛光压力是使用多孔填充的聚氨酯抛光垫压力垂直于晶片测得。优选地,该选自SiC,SiCN,Si3N4和SiCO至少一种的覆层是封盖层。就本说明书而言,可比的去除是指使用多孔填充的聚氨酯垫垂直于晶片测得的压力而得到的去除速率。用于测定选择性的特定抛光垫是IC1010TM多孔填充聚氨酯抛光垫。此外,该组合物可以在6.9kPa(1psi)下提供极好的选择性。因为该组合物会在各种抛光压力下起作用,这些数据用于说明该组合物的功效,而不是用来描述使用该组合物的具体操作压力。该抛光组合物可选具有至少2比1或至少5比1的TEOS相对于封盖层的选择性,该选择性使用多孔填充的聚氨酯抛光垫压力垂直于晶片测得且采用至少一种小于21.7kPa的抛光压力。所选的集成方案可控制TEOS的选择性。
除掩模层相对于封盖层的选择性之外,该溶液可选具有相对于金属互连的阻挡层去除选择性——使用垂直于晶片测得的多孔填充聚氨酯抛光垫压力且采用至少一种小于21.7kPa的抛光压力,该溶液能够以比金属互连例如铜更大的速率除去阻挡层物质。可选地,该抛光组合物具有大于或等于2比1的氮化钽相对铜的选择性,该选择性使用垂直于晶片测得的多孔填充聚氨酯抛光垫压力且采用至少一种小于21.7kPa的抛光压力测得。可选地,该抛光组合物具有大于或等于5比1的氮化钽相对铜的选择性,该选择性使用垂直于晶片测得的多孔填充聚氨酯抛光垫压力且采用至少一种小于21.7kPa的抛光压力测得。这种高水平的选择性允许芯片制造商从阻挡层上除去材料而不会除去过多的互连材料。
实施例
实施例1
PL150H25是来自Clariant的胶态氧化硅且包含30wt%的氧化硅颗粒,该氧化硅颗粒具有25nm的平均颗粒尺寸。
进行本实验以测定该抛光组合物在不同的组分浓度下的抛光性能。使用由Applied Materials提供的型抛光设备进行抛光实验。该抛光垫是由Rodel公司提供的IC1010TM多孔填充聚氨酯抛光垫。在每次实验(run)之前对该垫板进行调整。以6.9kPa(1psi)的压力,120转每分钟(rpm)的工作台转速和114rpm的托架转速进行该抛光过程。该抛光组合物的供给速率是180ml/min。
在下列实施例中应注意的是,字母表中的字母代表对比组合物,然而代表本抛光组合物的实施例用数字表示。在这个实施例中,使用氢氧化四甲铵和硝酸钾形成对比组合物来提供简单阳离子同具有烷基链的铵盐的去除速率的比较。因此在实施例1中,包含对照组成的试样A——不添加铵盐,包含硝酸钾的试样B-D和包含氢氧化四甲铵的试样E-G是对比组合物,而包含铵盐硝酸四乙铵(TEAN)的试样1-3,包含氟化四丁铵(TBAF)的试样4-6,和包含氢氧化四戊铵(TPAH)的试样7-9代表本抛光组合物。
制备表1中所示的几种抛光组合物以便在不同浓度水平的选定组分和2.5的pH下对抛光性能进行评价。在该抛光组合物的制备中,在容器中将表1所示的所有必需的化学物质按需要的数量(除过氧化氢和研磨剂以外)加入到去离子水中。对容器中的溶液进行搅拌直到所有的成分溶于水。然后通过添加硝酸将该溶液的pH调节至大约2.5。然后将研磨剂加入该容器。通过添加硝酸将该溶液最终的pH调节至2.5。此后,向该容器中加入过氧化氢从而用作抛光组合物。表1至5的试样全都包含0.6%的BTA,4%25nm的氧化硅(PL150H25)和0.5%的H2O2,以重量百分比计。
表1
试样 | 添加剂 | 添加剂按mM计 | 添加剂按wt%计 | TaNRR | CuRR | TEOSRR | SiCNRR | CDORR | ζ电位(mV) | 电导率(S/m) |
A | 808 | 190 | 59 | 537 | 109 | -10.17 | 0.14837 | |||
B | KNO3 | 1.56mM | 0.0158 | 1181 | 147 | 67 | 659 | 100 | -8.45 | 0.154805 |
C | KNO3 | 3.12mM | 0.0316 | 1100 | 107 | 76 | 592 | 90 | -7.31 | 0.162279 |
D | KNO3 | 5.21mM | 0.0526 | 1042 | 154 | 102 | 483 | 92 | -6.01 | 0.197874 |
E | TMAH | 1.56mM | 0.0142 | 1079 | 86 | 108 | 694 | 172 | -4.88 | 0.14435 |
F | TMAH | 3.12mM | 0.0284 | 989 | 90 | 152 | 256 | 138 | -2.11 | 0.15842 |
G | TMAH | 5.1mM | 0.0474 | 927 | 131 | 152 | 177 | 118 | -0.65 | 0.16718 |
1 | TEAN | 1.56mM | 0.03 | 873 | 70 | 204 | 86 | 119 | 1.83 | 0.14948 |
2 | TEAN | 3.12mM | 0.06 | 829 | 64 | 227 | 59 | 98 | 1.84 | 0.14948 |
3 | TEAN | 5.21mM | 0.1 | 784 | 70 | 169 | 50 | 87 | 6.93 | 0.16369 |
4 | TBAF | 1.56mM | 0.0492 | 946 | 71 | 447 | 55 | 56 | 9.26 | 0.14487 |
5 | TBAF | 3.12mM | 0.0984 | 918 | 84 | 467 | 42 | 45 | 11.74 | 0.14012 |
6 | TBAF | 5.21mM | 0.164 | 1026 | 141 | 415 | 41 | 38 | 14.64 | 0.13602 |
7 | TPAH | 1.56mM | 0.0493 | 707 | 102 | 209 | 79 | 116 | -2.47 | 0.14534 |
8 | TPAH | 3.12mM | 0.0986 | 600 | 76 | 265 | 99 | 70 | 5.12 | 0.15722 |
9 | TPAH | 5.21mM | 0.164 | 513 | 40 | 231 | 95 | 60 | 7.22 | 0.16381 |
TMAH:氢氧化四甲铵
TEAN:硝酸四乙铵
TBAF:氟化四丁铵
TPAH:氢氧化四戊铵
RR=以埃每分钟计的去除速率
表1的结果分别如图1和图2所示。图1是TEOS的去除速率与硝酸钾或铵盐的摩尔添加浓度的关系的图解表示(为了说明铵盐之间的差异,该图使用摩尔浓度而不是重量百分数)。图2是碳氮化硅(SiCN)的去除速率与硝酸钾或铵盐的摩尔添加浓度的关系的图解表示。图1和2显示,TEOS的去除速率随该铵盐的烷基链长度的增加而增加,一直到氟化四丁铵。对于所研究的所有铵盐,氟化四丁铵具有最高的TEOS去除速率和最低的SiCN去除速率。增加KNO3浓度时相对平坦的TEOS和SiCN去除速率表明该溶液的离子强度不会引起TEOS或SiCN的去除速率的显著变化。应注意的是,当使用相同的颗粒负载和抛光压力与其它商品浆料进行比较时,在该抛光处理条件下由TBAF得到的TEOS去除速率非常高。
实施例2
进行本实施例以便进一步证明高的TEOS去除速率不是由TBAF添加剂浆料中的氟离子引起。在这个实施例中,对比组合物H,I,和J包含氟离子。以氟化铵(NH4F)的形式将氟离子加入该抛光组合物。正如实施例1中所提到的,对比组合物A包含对照组成而没有任何氟离子。用试样#10表示该包含氟化四丁铵的抛光组合物。该抛光条件类似于实施1中的抛光条件。配方如表2所示。
试样 | 添加剂 | 添加剂按mM计 | 添加剂按wt%计 | TaNRR | CuRR | TEOSRR | SiCNRR | CDORR |
A | 653 | 109 | 41 | 614 | 138 | |||
H | NH4F | 1.56mM | 0.00578% | 1074 | 108 | 67 | 648 | 163 |
I | NH4F | 3.12mM | 0.0116% | 785 | 95 | 73 | 376 | 171 |
J | NH4F | 5.21mM | 0.0193% | 793 | 97 | 81 | 272 | 133 |
10 | TBAH | 1.56mM | 0.0492% | 816 | 72 | 518 | 78 | 77 |
以上数据非常明确地显示出,包含氟化铵的试样并不表现除高的TEOS去除速率,然而包含TBAF的试样表现出非常高的TEOS去除速率。此外,比较表1与表2的结果显示,虽然铵盐会影响TEOS和SiCN的去除速率,但半导体衬底中其它材料的去除速率的变化会减小到低的水平。这对于超低k集成电路的CMP是重要的。其允许不同的集成方案用于超低k CMP。
对于具有较高烷基链的化学物质,在一定浓度下该抛光组合物可能通过吸附到该颗粒的表面并使其带正电,从而将氧化硅的ζ电位改变到较高值。这种组合物还可以影响TEOS和封盖层上的表面电荷,使得氧化硅研磨剂和集成电路上的TEOS层之间的电荷排斥减小,而相应的氧化硅和封盖层之间的电荷排斥增加。上面的表2和表3中显示了不同四铵盐对氧化硅ζ电位的影响。
图3是初始抛光组合物的ζ电位与硝酸钾或铵盐浓度的关系的图解表示。上述的曲线图显示,TBAF对氧化硅的ζ电位具有最大的影响,在所有的铵盐中TBAF将电荷提高到最大的正值。因此,TBAF产生了最高的TEOS去除速率和最低的SiCN去除速率。
实施例3
进行本实施例以便确定不同离子对集成电路的TEOS掩模的去除速率的影响。使用由Applied Materials提供的Mirra型抛光设备进行抛光实验。抛光垫是由Rodei公司提供的PiitexTM垫。在每次实验之前对该垫进行调整。以10.33kPa(1.5psi)的膜压,93转每分钟(rpm)的工作台转速和87rpm的托架转速进行该抛光处理。该抛光组合物的供给速率是180ml/min。
在这个实验中,试样A代表对照组合物。然而使用硝酸四丁铵的试样11-16和使用氟化四丁铵的试样17-22代表抛光组合物。相应的实验组合物及结果如下表3所示。
表3
试样 | TBANmM | TBANwt% | TBAFmM | TBAFwt% | TaNRR | CuRR | TEOSRR | SiCNRR | CDORR |
A | 1453 | 186 | 81 | 795 | 238 | ||||
11 | 0.317 | 0.00965 | 1346 | 84 | 131 | 654 | 441 | ||
12 | 0.951 | 0.0290 | 1334 | 82 | 279 | 217 | 276 | ||
13 | 1585 | 0.0483 | 1358 | 76 | 441 | 145 | 183 | ||
14 | 3.17 | 0.0965 | 1396 | 75 | 561 | 99 | 112 | ||
15 | 6339 | 0.193 | 1304 | 92 | 500 | 91 | 108 | ||
16 | 12.678 | 0.386 | 1312 | 153 | 394 | 84 | 77 | ||
17 | 0.317 | 0.01 | 1333 | 97 | 164 | 483 | 367 | ||
18 | 0.951 | 0.03 | 1420 | 89 | 525 | 138 | 175 | ||
19 | 1.585 | 0.05 | 1461 | 89 | 696 | 104 | 124 | ||
20 | 3.17 | 0.1 | 1573 | 108 | 787 | 85 | 102 | ||
21 | 6339 | 0.2 | 1659 | 149 | 633 | 72 | 96 | ||
22 | 12.678 | 0.4 | 1859 | 188 | 397 | 74 | 104 |
TBAF:氟化四丁铵
BTAN:硝酸四丁铵
上述数据显示,当使用氟离子替代铵盐中的硝酸根离子时,TEOS的去除速率相对更高。此外,提高氟化四丁铵的浓度可提高阻挡层(TaN)的去除速率,然而硝酸四丁铵未显示出对TaN去除速率的明显影响。下面在图4和图5中分别图解显示了TBAN和TBAF对TEOS和TaN去除速率的比较。该数据显示,当与表2中所示的TEOS层去除速率比较时,当氟离子以季铵盐的形式存在时,氟离子在TEOS和TaN层的去除速率中起重要作用。
实施例4
进行本实施例以说明其它铵盐的使用,例如氯化苄基三丁铵(BTBAC),氯化苄基三甲铵(BTMAC),氯化苄基三乙铵(BTEAC)。试样A代表对照组合物,而包含BTBAC的试样23-25,包含BTMAC的试样26-28和包含BTEAC的试样29-30代表本抛光组合物。
使用由Strasbaugh提供的型号为6EC的抛光设备进行抛光实验。抛光垫是由Rodel公司提供的IC1010TM垫。在每次实验之前对该垫板进行调整。以10.33kPa(1.5psi)的垫压力,93转每分钟(rpm)的工作台转速和87rpm的托架转速进行该抛光处理。该抛光组合物的供给速率是200ml/min。结果如下表4所示。
表4
试样 | 添加剂 | 添加剂按mM计 | 添加剂按wt%计 | TaNRR | CuRR | TEOSRR | CDORR | Si3N4RR | SiCNRR |
A | 1438 | 72 | 102 | 244 | 523 | 1030 | |||
23 | BTBAC | 0.95mM | 0.0283% | 1176 | 63 | 543 | 174 | 172 | 227 |
24 | BTBAC | 3.17mM | 0.0943% | 1123 | 85 | 714 | 102 | 91 | 187 |
25 | BTBAC | 12.7mM | 0.377% | 1193 | 96 | 462 | 88 | 66 | 143 |
26 | BTMAC | 0.95mM | 0.0231% | 1179 | 63 | 366 | 264 | 259 | 384 |
27 | BTMAC | 3.17mM | 0.0769% | 1148 | 70 | 483 | 162 | 110 | 201 |
28 | BTMAC | 12.7mM | 0.0307% | 1065 | 75 | 245 | 130 | 94 | 89 |
29 | BTEAC | 0.95mM | 0.0169% | 1198 | 53 | 528 | 214 | 230 | 306 |
30 | BTEAC | 3.17mM | 0.0563% | 466 | 70 | 641 | 135 | 34 | 202 |
BTBAC:氯化苄基三丁铵
BTMAC:氯化苄基三甲铵
BTEAC:氯化苄基三乙铵
由上表可以看出,可以使用这些铵盐来改变掩模层例如TEOS和封盖层例如氮化硅(Si3N4)和SiCN的去除速率,然而仍保持阻挡层例如试样23-29中的TaN的去除速率相对不变。
实施例5
本实施例用于说明部分氢取代铵盐例如三亚乙基四胺,四甲胍和己胺的使用。试样A代表用作比较的对照组合物,而包含三亚乙基四胺的试样31-32,包含四甲胍的试样33-34,包含己胺的试样35-36和包含TBAN的试样37代表抛光组合物。
使用由Strasbaugh提供的型号为6EC的抛光设备进行抛光实验。抛光垫是由Rodel公司提供的IC1010TM多孔填充聚氨酯抛光垫。在每次实验之前对该垫进行调整。以10.33kPa(1.5psi)的背压,93转每分钟(rpm)的工作台转速和87rpm的托架转速进行该抛光处理。该抛光组合物的供给速率是200ml/min。结果如下表5所示。
表5
试样 | 添加剂 | 添加剂按mM计 | 添加剂按wt%计 | TaNRR | CuRR | TEOSRR | CDORR | Si3N4RR | SiCNRR |
A | 1438 | 72 | 102 | 244 | 523 | 1030 | |||
31 | 三亚乙基四胺 | 4.9mM | 0.1% | 1283 | - | 312 | 262 | 242 | - |
32 | 三亚乙基四胺 | 24.48mM | 0.5% | 1480 | 134 | 308 | 222 | 283 | 400 |
33 | 四甲胍 | 0.868mM | 0.01% | 1259 | 75 | 409 | 194 | 102 | 295 |
34 | 四甲胍 | 86.8mM | 1% | 1251 | 104 | 212 | 149 | 95 | 161 |
35 | 己胺 | 19.76mM | 0.2% | 1200 | 87 | 280 | - | 107 | 277 |
36 | 己胺 | 59.29mM | 0.6% | 1278 | 100 | 251 | - | 92 | 213 |
37 | 硝酸四丁氨 | 3.284mM | 0.1% | 1447 | 68 | 765 | - | 80 | 72 |
从上表可以看出,由这些胺类化合物形成的氨盐也可以用于改变掩模层例如TEOS和封盖层例如氮化硅(Si3N4)和SiCN的去除速率,然而仍保持阻挡层例如试样31-36中的TaN的去除速率相对不变。虽然由这些胺类化合物形成的铵盐具有有效的去除速率,如上所示,四丁铵盐(试样37)具有更高的TEOS去除速率和TEOS相对封盖层的选择性。
实施例6
在由Applied Materials提供的Mirra型抛光设备上进行本实验。抛光垫是由Rodel公司提供IC1010TM。在每次实验之前对垫板进行调整。以10.3kPa(1.5psi)的压力,93转每分钟(rpm)的工作台转速和87rpm的托架转速进行该抛光处理。该CMP组合物的供给速率(浆料流量)是200毫升/分钟(ml/min)。首先通过可商购的浆料EPL2362(Eternal),且使用CUP4410垫(由Rodel公司提供)和3psi,93rpm的工作台转速,87rpm的托架转速和200ml/min的浆料流量的工艺参数对用于缺陷测试的薄铜板晶片进行预抛光1分钟。这个步骤用来形成新鲜的铜表面。然后用浆料组合物16和常规的碱性浆料对预抛光的薄铜板晶片进行抛光。
表6
微划痕 | 大划痕 | 全部检查数目 | |
碱性浆料 | 2740 | 170 | 2989 |
组合物16 | 114 | 142 | 355 |
表6显示了,用组合物16抛光的薄铜板晶片的缺陷数显著少于常规碱性浆料的缺陷数。图6说明了所得缺陷的显著改善。
从上面的实验可以看出,当与阻挡层的去除速率比较时,抛光组合物中铵盐的使用对于包含氧化硅的层可容许不同的去除速率。这有利于容许一个层相对于另一层的快速去除,例如TEOS相对SiCN。例如,对于具有掩模层和封盖层的半导体,其可容许掩模层相对于封盖层的选择性大于或等于3比1或甚至大于或等于10比1。该选择比适用于沉积在SiC,SiCO,Si3N4或SiCN封盖层上的TEOS掩模。该选择比也适用于下面的表6中所示的单一掩模。也可以对该抛光组合物进行调整以便去除含氧化硅的层而不对低k或超低k介电层造成任何破坏。下表7显示了这些抛光组合物去除半导体衬底上的各种层而不对含氧化硅的层,低k和/或超低k介电层造成任何破坏的性能。
表7
集成方案# | 层 | 互连结构 | 用于CMP的集成方案 | 去除速率(RR)要求 |
1 | 双重覆层 | TaN/TEOS/SiCN/低k或超低k介电层 | 抛光TaN和TEOS层;在SiCN和低k或超低k介电层上停止抛光 | 高的TaN和TEOS去除速率;低的SiCN和低k或超低k介电层去除速率 |
2 | 单一覆层 | TaN/TEOS(或SiCN)/低k或超低k介电层 | 抛光TaN和TEOS(或SiCN);在低k或超低k介电层上停止抛光 | 高的TaN和TEOS(或SiCN)层去除速率;低的低k或超低k介电层去除速率 |
3 | 单一覆层 | TaN/TEOS(或SiCN)/低k或超低k介电层 | 抛光TaN层;在TEOS(或SiCN)和低k或超低k介电层上停止抛光 | 高的TaN去除速率;低的TEOS(或SiCN)和低k或超低k介电层去除速率 |
4 | 无覆层 | TaN/低k或超低k介电层 | 抛光TaN层;在低k或超低k介电层上停止抛光 | 高的TaN去除速率;低的低k或超低k介电层去除速率 |
表7显示了可以用于从半导体衬底上选择性去除某些所需层的多种集成方案。例如,集成方案1显示了如何利用该抛光组合物来从分别包含TaN,TEOS,SiCN和超低k介电层的互连结构上选择性去除TaN和TEOS层。该抛光组合物以相对于SiCN和CDO层更高的速率除去TaN和TEOS层,从而保留该SiCN和超低k介电层。
可以使用该抛光组合物来调节从集成电路器件的互连结构上去除含氧化硅层和阻挡层的去除速率。可以对其进行调节或调整以便获得高的含氧化硅层去除速率,同时具有减小的互联金属凹陷或者在例如SiCN的封盖层上停止。可选地,该方法包括在去除含氧化硅层之前使用该水性抛光组合物除去阻挡层。此外,如果含氧化硅层是沉积在底层上的顶部TEOS层且该底层是SiC,SiCN,Si3N4或SiCO,这时该组合物可以除去顶层而留下至少一部分底层。这种选择性TEOS去除对于保护具有封盖层的低k和超低k电介质特别有效。
Claims (4)
1.水性抛光组合物,以重量百分数计,所述组合物包含:
具有用硝酸、硫酸、盐酸或磷酸调节的2-4的酸性pH;
0.05-15的胶态二氧化硅研磨剂颗粒;
0.1-5的过氧化氢;
0.25-1苯并三唑;以及
0.001-3的包含有机物的铵盐,所述包含有机物的铵盐选自硝酸四乙铵,氟化四丁铵和它们的混合物。
2.权利要求1的组合物,其中该抛光组合物具有用硝酸调节的pH。
3.用于从半导体衬底上去除一层的方法,该方法包括:
将水性抛光组合物涂覆到该半导体衬底上,该水性抛光组合物包含权利要求1所述的组合物;和
用抛光垫对含氧化硅层进行抛光,以便从该半导体衬底上除去该含氧化硅层。
4.权利要求3的方法,该方法包括在去除含氧化硅层之前使用该水性抛光组合物抛光阻挡层的另外的步骤。
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CN1609156A (zh) | 2005-04-27 |
DE602004012674T2 (de) | 2009-04-09 |
TW200513523A (en) | 2005-04-16 |
EP1505133A1 (en) | 2005-02-09 |
KR20050016128A (ko) | 2005-02-21 |
JP2005101545A (ja) | 2005-04-14 |
US7018560B2 (en) | 2006-03-28 |
TWI365907B (en) | 2012-06-11 |
KR101092939B1 (ko) | 2011-12-12 |
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