JP5381701B2 - 金属用研磨液及び研磨方法 - Google Patents
金属用研磨液及び研磨方法 Download PDFInfo
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- JP5381701B2 JP5381701B2 JP2009501221A JP2009501221A JP5381701B2 JP 5381701 B2 JP5381701 B2 JP 5381701B2 JP 2009501221 A JP2009501221 A JP 2009501221A JP 2009501221 A JP2009501221 A JP 2009501221A JP 5381701 B2 JP5381701 B2 JP 5381701B2
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- Prior art keywords
- metal
- polishing
- abrasive grains
- film
- polishing liquid
- Prior art date
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UKKHWKNEQBGLMI-UHFFFAOYSA-N n-pyrimidin-2-ylacetamide Chemical compound CC(=O)NC1=NC=CC=N1 UKKHWKNEQBGLMI-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 229920003175 pectinic acid Polymers 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- MQEFDQWUCTUJCP-UHFFFAOYSA-N pyrimidine-2,4,5,6-tetramine;sulfuric acid Chemical compound OS(O)(=O)=O.NC1=NC(N)=C(N)C(N)=N1 MQEFDQWUCTUJCP-UHFFFAOYSA-N 0.000 description 1
- YAAWASYJIRZXSZ-UHFFFAOYSA-N pyrimidine-2,4-diamine Chemical compound NC1=CC=NC(N)=N1 YAAWASYJIRZXSZ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- POFDSYGXHVPQNX-UHFFFAOYSA-N triazolo[1,5-a]pyrimidine Chemical compound C1=CC=NC2=CN=NN21 POFDSYGXHVPQNX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- C09G—POLISHING COMPOSITIONS; SKI WAXES
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- 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
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- C23F1/26—Acidic compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
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- 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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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
- H01L21/04—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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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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
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
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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
- H01L21/04—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
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Description
(研磨液作製方法)
表1に示す材料をそれぞれの配合(質量部)で混合して、実施例1〜8及び比較例1〜2に使用する金属用研磨液を調製した。この金属用研磨液を用いて下記の研磨条件で、下記で得た基板の研磨を行った。
砥粒の平均2次粒径は、動的散乱法に基づいたサブミクロン粒子アナライザー(BECKMAN COULTER社製、機種名:N5 Submicron Particle Size Analyzer)を用いて測定した。
砥粒の平均1次粒径は、超高分解能電子顕微鏡(SEM)(日立協和エンジニアリング株式会社製、機種名:日立 S−4800)を用いて撮影し大きさを実測した。
以下の基板を用意した。
ブランケット基板(a1):シリコン基板上にトリメチルシランを出発原料としてCVD法で成膜されたオルガノシリケートグラス(厚さ:1000nm)を形成。
パターン基板(b1):シリコン基板上に層間絶縁膜としてトリメチルシランを出発原料としたオルガノシリケートグラスをCVD法で成膜した。このオルガノシリケートグラスに公知の方法を用いて深さ0.5μmの溝(凹部)を形成して、この表面に沿ってスパッタ法により金属バリア層として厚さ200nmのタンタル膜を形成した。前記タンタル膜の上に、スパッタ法により前記溝を埋めるように導電性物質層として銅膜を1.0μm形成した。突出している該銅膜だけをシリカ系研磨液(日立化成社製、製品名:HS-C500-10)を用いて第1のCMP工程における研磨を行い、被研磨面に凸部のバリア層を露出させ、パターン基板(b1)を得た。
研磨パッド:発泡ポリウレタン樹脂(ロデール社製、型番:IC1000)
研磨圧力:140g/cm2(13.73kPa)
研磨定盤及びウエハホルダーの回転数:90rpm
研磨液の供給量:150ml/min
(評価項目)
(1)研磨速度:各ブランケット基板(a1)〜(a4)を上記条件で、金属用研磨液を用い60秒研磨した。オルガノシリケートグラス及び二酸化ケイ素の研磨速度は研磨前後での膜厚差を大日本スクリーン製造株式会社製、膜厚測定装置(製品名:ラムダエース)を用いて測定し求めた。また、タンタル及び銅の研磨速度は研磨前後での膜厚差を電気抵抗値から換算して求めた。
コロイダルシリカB:平均2次粒径:28nm、平均1次粒径:13nm
コロイダルシリカC:平均2次粒径:50nm、平均1次粒径:26nm
コロイダルシリカD:平均2次粒径:70nm、平均1次粒径:43nm
コロイダルシリカE:平均2次粒径:90nm、平均1次粒径:50nm
比較例1及び比較例2では、層間絶縁膜であるオルガノシリケートグラス又は二酸化ケイ素を形成したブランケット基板(a1)又は(a2)に対する研磨速度が小さいためにディッシング量及びエロージョン量が大きくなっている。それに対し、実施例1〜8では、層間絶縁膜であるオルガノシリケートグラス又は二酸化ケイ素を形成したブランケット基板(a1)又は(a2)に対する研磨速度が大きいため、ディッシング量及びエロージョン量が少ない。この実施例で見出したような金属用研磨液は、微細化、薄膜化、寸法精度、電気特性に優れ、信頼性が高く、低コストの可能であることが分かった。
【産業上の利用可能性】
Claims (14)
- 金属バリア層及び層間絶縁膜を含む被研磨膜を研磨するための金属用研磨液であって、
前記層間絶縁膜が、シリコン系被膜又は有機ポリマ膜であり、
砥粒としてシリカと、酸化金属溶解剤と、水を含有し、
前記砥粒が、平均2次粒径5〜39nmの第一の砥粒と平均2次粒径40〜90nmの第二の砥粒とを含み、
pHが2〜5である金属用研磨液。 - 前記砥粒が、前記第一の砥粒を砥粒全体に対して1〜50質量%、前記第二の砥粒を砥粒全体に対して50〜99質量%含む請求項1記載の金属用研磨液。
- 前記砥粒が、平均1次粒径2〜50nmの砥粒を含む請求項1又は2記載の金属用研磨液。
- 前記酸化金属溶解剤が、有機酸、有機酸エステル、有機酸のアンモニウム塩及び無機酸から選ばれる少なくとも1種である請求項1〜3のいずれか一項記載の金属用研磨液。
- さらに金属の酸化剤を含有する請求項1〜4のいずれか一項記載の金属用研磨液。
- 前記金属の酸化剤が、過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸及びオゾン水から選ばれる少なくとも1種である請求項5記載の金属用研磨液。
- さらに金属防食剤を含有する請求項1〜6のいずれか一項記載の金属用研磨液。
- 重量平均分子量が500以上500万以下のポリマをさらに含有する請求項1〜7のいずれか一項に記載の金属用研磨液。
- 金属用研磨液によって研磨される被研磨膜が、さらに導電性物質層を含む被研磨膜である請求項1〜8のいずれか一項記載の金属用研磨液。
- 前記導電性物質層が、銅、銅合金、銅の酸化物及び銅合金の酸化物から選ばれる少なくとも1種から成る層である請求項9記載の金属用研磨液。
- 前記金属バリア層が、タンタル、タンタル化合物、チタン、チタン化合物、タングステン、タングステン化合物、ルテニウム、ルテニウム化合物、銅とマンガンとの合金、銅とマンガンと酸化ケイ素との合金から選ばれる少なくとも1種からなる1層、又は2層以上の積層である、請求項1〜10のいずれか一項記載の金属用研磨液。
- 前記砥粒は、金属用研磨液の総量100質量部に対して、0.001〜50質量部である請求項1〜11のいずれか一項に記載の金属用研磨液。
- 導電性物質層と層間絶縁膜の研磨速度比が0.72以下である請求項9〜12のいずれか一項に記載の金属用研磨液。
- 研磨定盤の研磨布上に請求項1〜13のいずれか一項記載の金属用研磨液を供給しながら、被研磨膜を有する基板を研磨布に押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨する研磨方法。
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S533 | Written request for registration of change of name |
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R350 | Written notification of registration of transfer |
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S531 | Written request for registration of change of domicile |
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R350 | Written notification of registration of transfer |
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