JP2017157591A - Cmp研磨液及び研磨方法 - Google Patents
Cmp研磨液及び研磨方法 Download PDFInfo
- Publication number
- JP2017157591A JP2017157591A JP2016036880A JP2016036880A JP2017157591A JP 2017157591 A JP2017157591 A JP 2017157591A JP 2016036880 A JP2016036880 A JP 2016036880A JP 2016036880 A JP2016036880 A JP 2016036880A JP 2017157591 A JP2017157591 A JP 2017157591A
- Authority
- JP
- Japan
- Prior art keywords
- polishing liquid
- cobalt
- carboxylic acid
- polishing
- cmp polishing
- 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.)
- Granted
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 285
- 239000007788 liquid Substances 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 91
- 239000010941 cobalt Substances 0.000 claims abstract description 91
- -1 aromatic carboxylic acid compound Chemical class 0.000 claims abstract description 61
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 64
- 239000006061 abrasive grain Substances 0.000 claims description 23
- 150000007524 organic acids Chemical class 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 23
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 description 53
- 239000000758 substrate Substances 0.000 description 36
- 239000011810 insulating material Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 229910052721 tungsten Inorganic materials 0.000 description 18
- 239000010937 tungsten Substances 0.000 description 18
- 229910000531 Co alloy Inorganic materials 0.000 description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 14
- 229910000881 Cu alloy Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229910001080 W alloy Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
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- 239000000377 silicon dioxide Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000003851 azoles Chemical class 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 150000001869 cobalt compounds Chemical class 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 150000003222 pyridines Chemical class 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000003482 tantalum compounds Chemical class 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 150000003658 tungsten compounds Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 229910000929 Ru alloy Inorganic materials 0.000 description 4
- 229910001362 Ta alloys Inorganic materials 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000003304 ruthenium compounds Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
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- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
上記アルキル基の炭素数は1〜3であってもよい。
上記芳香族カルボン酸化合物は4−メチルフタル酸又はその塩であってもよい。
上記CMP研磨液は、砥粒を更に含有していてもよい。
上記CMP研磨液は、上記芳香族カルボン酸化合物以外の有機酸成分を更に含有していてもよい。
上記CMP研磨液は、金属酸化剤を更に含有していてもよい。
上記CMP研磨液は、金属防食剤を更に含有していてもよい。
上記CMP研磨液は、有機溶媒を更に含有していてもよい。
「エッチング速度」とは、研磨される物質Aが研磨液に溶解する速度(例えば、時間当たりの物質Aの厚みの低減量(Etching Rate))を意味する。
「工程」には、独立した工程だけではなく、他の工程と明確に区別できない場合であっても、当該「工程」において規定される操作が実施される限り、他の工程と明確に区別できない工程も含まれる。
「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
CMP研磨液中の各成分の含有量は、CMP研磨液中に各成分に該当する物質が複数存在する場合、特に断らない限り、CMP研磨液中に存在する当該複数の物質の合計量を意味する。
「コバルト含有部」とは、コバルト原子を含む部分を意味し、「コバルト含有部」には、例えば、コバルト、コバルト合金、コバルトの酸化物、コバルト合金の酸化物等を含有する部分が含まれる。
「銅含有部」とは、銅原子を含む部分を意味し、「銅含有部」には、例えば、銅、銅合金、銅の酸化物、銅合金の酸化物等を含有する部分が含まれる。
本実施形態のCMP研磨液は、コバルト研磨用CMP研磨液である。上記CMP研磨液は、例えば、コバルト含有部を研磨するために用いることができる。本実施形態のCMP研磨液は、カルボン酸基(以下、場合により「カルボキシ基」ともいう)及びカルボン酸塩基の合計が2である芳香族カルボン酸化合物と、水と、を含有し、上記芳香族カルボン酸化合物が、一のカルボン酸基又はカルボン酸塩基のオルト位に他のカルボン酸基又はカルボン酸塩基が結合した構造を有し、pHが4.0を超えるものである。このようなCMP研磨液によれば、コバルト含有部のエッチング速度を抑制できる。また、本実施形態のCMP研磨液によれば、コバルト含有部の研磨速度を良好な範囲に保ちつつ、エッチング速度を抑制することができる。
本実施形態のCMP研磨液は、砥粒(研磨粒子)を更に含有していてもよい。CMP研磨液が砥粒を含有することにより、金属含有部(例えば、コバルト含有部の近傍に設けられた金属含有部)の研磨速度が更に向上する傾向がある。砥粒は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、カルボン酸基及びカルボン酸塩基の合計が2である芳香族カルボン酸化合物を含有する。当該芳香族カルボン酸化合物は、一のカルボン酸基又はカルボン酸塩基のオルト位に他のカルボン酸基又はカルボン酸塩基が結合した構造を有するものである。なお、上記芳香族カルボン酸化合物が有し得るカルボン酸基及びカルボン酸塩基は、芳香環に結合している。このような芳香族カルボン酸化合物は、コバルト含有部に対する錯化剤として機能すると推測される。カルボン酸塩基の塩としては、カリウム、アンモニウム等が挙げられる。上記芳香族カルボン酸化合物は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、上記芳香族カルボン酸化合物以外の有機酸成分を含有していてもよい。有機酸成分は、コバルト含有部及び金属含有部の研磨速度を更に向上させる効果を有する。有機酸成分としては、例えば、有機酸、並びに当該有機酸の塩、無水物、及びエステル化物が挙げられる。有機酸成分は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、金属防食剤を含有していてもよい。CMP研磨液が金属防食剤を含有することにより、コバルト含有部に対し、良好な研磨速度を保ちながら腐食を効果的に抑制できる。金属防食剤は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、金属酸化剤を含有していてもよい。金属酸化剤としては、特に制限はないが、例えば、過酸化水素、ペルオキソ硫酸塩、硝酸、過ヨウ素酸カリウム、次亜塩素酸、及びオゾンが挙げられる。金属酸化剤は、金属含有部の研磨速度を向上させる観点から、例えば、過酸化水素であってもよい。金属酸化剤は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、有機溶媒(上記芳香族カルボン酸化合物及び有機酸成分に該当する化合物を除く)を含有してもよい。CMP研磨液が有機溶媒を含有することにより、金属含有部(例えば、コバルト含有部の近傍に設けられた金属含有部)に対する、CMP研磨液の濡れ性を向上させることができる。有機溶媒としては、特に制限はないが、水と混合できるものが好ましく、25℃において、水100gに対して0.1g以上溶解するものがより好ましい。有機溶媒は、一種を単独で、又は二種以上を混合して用いることができる。
本実施形態のCMP研磨液は、得られる効果等を考慮し、前述の成分以外の任意の成分を含有することもできる。任意の成分としては、例えば、一般的な金属用研磨液に用いられる分散剤、界面活性剤、水溶性ポリマ等の添加剤が挙げられる。
CMP研磨液は水を含有する。水は、特に制限されるものではないが、純水を好ましく用いることができる。水は残部として配合されていればよく、含有量に特に制限はない。
本実施形態のCMP研磨液のpHは、4.0を超えるものである。上記CMP研磨液のpHは、コバルト含有部のエッチングを更に抑制する観点から、4.5以上であることが好ましく、5.0以上であることがより好ましく、5.5以上であることが更に好ましい。上記CMP研磨液のpHは、コバルト含有部の研磨速度を更に良好な範囲に保つ観点から、10.5以下であることが好ましく、9.5以下であることがより好ましく、8.0以下であることが更に好ましい。
本実施形態のCMP研磨液は、複数の添加液を混合して上記研磨液となるように、上記研磨液の構成成分を複数の添加液に分けた複数液式の研磨液セットとして保存してもよい。本実施形態のCMP研磨液が砥粒を含有する場合、CMP研磨液は、例えば、スラリと添加液とを混合して上記研磨液となるように、上記研磨液の構成成分をスラリと添加液とに分けた複数液式(例えば、二液式)の研磨液セットとして保存してもよい。上記研磨液セットは、例えば、砥粒及び水を含むスラリと、本実施形態に係る芳香族カルボン酸化合物、必要に応じ金属酸化剤等を含む添加液とに分けた形態であってもよい。
本実施形態の研磨方法は、上述した本実施形態のCMP研磨液を用いて、コバルトを含む被研磨面を研磨する研磨方法である。コバルトを含む被研磨面は、例えば、コバルト含有部である。本実施形態のCMP研磨液を、コバルトを含む被研磨面の研磨に用いると、コバルトを含む被研磨面を良好な研磨速度で研磨できるとともに、コバルトのエッチングを抑制できる。上記被研磨面は、コバルト以外の金属からなる金属含有部を有してもよい。すなわち、本実施形態の研磨方法は、本実施形態のCMP研磨液を用いて、コバルト含有部とコバルト以外の金属からなる金属含有部とを有する被研磨面を研磨する方法であってもよい。本実施形態の研磨方法は、本実施形態のCMP研磨液を用いて、コバルト含有部を有し、かつ、主たる成分として銅を含有する銅含有部を有しない被研磨面の、コバルト含有部の少なくとも一部を研磨して除去する研磨方法であってもよい。また、被研磨面には、後述する絶縁材料部が含まれていてもよい。
表1〜5に示す各成分を用いてCMP研磨液を下記の方法で作製した。
表1〜5に示す種類の砥粒と、芳香族ジカルボン酸と、有機酸成分と、金属防食剤と、有機溶媒と、添加剤とを容器に入れ、さらに、超純水を注ぎ、撹拌により混合して全成分を溶解させた。次いで、酸化剤として過酸化水素水(30質量%水溶液)を添加した後、超純水を加えて全体を100質量部としてCMP研磨液を得た。
CMP研磨液のpHを下記に従って測定した。
測定温度:25℃
測定器:株式会社堀場製作所製「pHMeter F−51」
測定方法:標準緩衝液(フタル酸塩pH緩衝液 pH:4.01(25℃)、中性リン酸塩pH緩衝液 pH:6.86(25℃)、ホウ酸塩pH緩衝液 pH:9.18(25℃)を用いて3点校正した後、電極をCMP研磨液に入れて、3min以上経過して安定した後の値を測定した。結果は表1〜5に示す。
以下の項目により、実施例1〜19及び比較例1〜4のCMP研磨液の評価を行った。
得られた各研磨液を用いて、以下の条件で被研磨基板を研磨し、研磨前後のコバルト層の厚みの差を研磨時間で割ることでコバルト研磨速度を算出した。なお、研磨前後のコバルト層の厚みは、電気抵抗力(抵抗値)を測定し当該測定値から換算する方法により算出した。抵抗値の測定には、ナプソン株式会社製、金属膜厚測定装置「RT−70」を用いた。算出されたコバルト研磨速度(Co−RR)[nm/min]は、表1〜5に示す。
(研磨条件)
被研磨基板:シリコン基板(直径8インチウエハ)に厚さ200nmのコバルト層を形成して得られたブランケット基板を切断して得た、20mm×20mmのチップ
研磨装置:日本エンギス株式会社製 IMPTECH 10DVT
研磨パッド:発泡ポリウレタン樹脂製の研磨パッド
定盤回転数:90min−1
研磨圧力:33.1kPa(4.8psi)
CMP研磨液の供給量:15mL/min
研磨時間:1min
得られた各研磨液に、以下の条件で基板を浸漬し、浸漬前後のコバルト層の厚みの差を浸漬時間で割ることでコバルトエッチング速度を算出した。なお、浸漬前後のコバルト層の厚みは、電気抵抗力(抵抗値)を測定し当該測定値から換算する方法により算出した。抵抗値の測定には、ナプソン株式会社製、金属膜厚測定装置「RT−70」を用いた。算出されたコバルトエッチング速度(Co−ER)[nm/min]は、表1〜5に示す。
(浸漬条件)
基板:シリコン基板(直径8インチウエハ)に厚さ200nmのコバルト層を形成して得られたブランケット基板を切断して得た、20mm×20mmのチップ
研磨液容量:100mLビーカー内の100mL
研磨液の温度:60℃
攪拌速度:200min−1
浸漬時間:5min
Claims (10)
- カルボン酸基及びカルボン酸塩基の合計が2である芳香族カルボン酸化合物と、水と、を含有し、
前記芳香族カルボン酸化合物が、一のカルボン酸基又はカルボン酸塩基のオルト位に他のカルボン酸基又はカルボン酸塩基が結合した構造を有し、
pHが4.0を超える、コバルト研磨用CMP研磨液。 - 前記芳香族カルボン酸化合物が、芳香環の1位及び2位のそれぞれにカルボン酸基又はカルボン酸塩基を有し、かつ、芳香環の4位にアルキル基を有する、請求項1に記載のCMP研磨液。
- 前記アルキル基の炭素数が1〜3である、請求項2に記載のCMP研磨液。
- 前記芳香族カルボン酸化合物が4−メチルフタル酸又はその塩である、請求項1〜3のいずれか一項に記載のCMP研磨液。
- 砥粒を更に含有する、請求項1〜4のいずれか一項に記載のCMP研磨液。
- 前記芳香族カルボン酸化合物以外の有機酸成分を更に含有する、請求項1〜5のいずれか一項に記載のCMP研磨液。
- 金属酸化剤を更に含有する、請求項1〜6のいずれか一項に記載のCMP研磨液。
- 金属防食剤を更に含有する、請求項1〜7いずれか一項に記載のCMP研磨液。
- 有機溶媒を更に含有する、請求項1〜8のいずれか一項に記載のCMP研磨液。
- 請求項1〜9のいずれか一項に記載のCMP研磨液を用いて、コバルトを含む被研磨面を研磨する、研磨方法。
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