JP2013102051A - 研磨用組成物並びにそれを用いた研磨方法及び基板の製造方法 - Google Patents
研磨用組成物並びにそれを用いた研磨方法及び基板の製造方法 Download PDFInfo
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- JP2013102051A JP2013102051A JP2011244784A JP2011244784A JP2013102051A JP 2013102051 A JP2013102051 A JP 2013102051A JP 2011244784 A JP2011244784 A JP 2011244784A JP 2011244784 A JP2011244784 A JP 2011244784A JP 2013102051 A JP2013102051 A JP 2013102051A
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
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- 150000005054 naphthyridines Chemical class 0.000 description 1
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- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000000561 purinyl group Chemical class N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 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
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 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
- 229960001367 tartaric acid Drugs 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 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 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-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
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
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- C09K13/00—Etching, surface-brightening or pickling compositions
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Abstract
【解決手段】本発明は、導体層と前記導体層と接する導電性物質層を有する研磨対象物を研磨する用途で使用される研磨用組成物であって、常温の研磨用組成物中で電位計の正極側を導電性物質に接続し、且つ負極側を導体に接続した条件において、導電性物質と導体を研磨したときに正極側から負極側へ流れる電流の値が、正の値(ゼロを含む。)を示すことを特徴とする研磨用組成物を提供する。さらには、研磨用組成物は、導体及び導電性物質との間に流れる電流値を正の値(ゼロを含む。)にする添加剤を含有することが好ましい。
【選択図】図1
Description
<1>導体層と前記導体層と接する導電性物質層を有する研磨対象物を研磨する用途で使用される研磨用組成物であって、常温の前記研磨用組成物中で電位計の正極側を前記導電性物質に接続し、且つ負極側を前記導体に接続した条件において、前記導電性物質と前記導体を研磨したときに正極側から負極側へ流れる電流の値が、正の値(ゼロを含む。)を示すことを特徴とする研磨用組成物。
<2>導体及び導電性物質との間に流れる電流値を正の値(ゼロを含む。)にする添加剤を含有する。
<3>電流値を正の値(ゼロを含む。)にする添加剤が、窒素原子含有化合物、硫黄原子含有化合物及びリン原子含有化合物からから選ばれるいずれか一以上である。
<4>導体が、貴金属を含む。
<5>導体が、ルテニウムを含む。
<6>前記<1>〜<5>のいずれかに記載の研磨用組成物を用いて、導体層とその導体層と接する導電性物質層を有する研磨対象物の表面を研磨することを含む研磨方法。
<7>前記<6>に記載の研磨用組成物を用いて、導体層とその導体層と接する導電性物質層を有する基板を得るべく、導体層とその導体層と接する導電性物質層を有する研磨対象物の表面を研磨して導体層とその導体層と接する導電性物質層の一部を除去することを含む、導体層とその導体層と接する導電性物質層を有する基板の製造方法。
本実施形態の研磨用組成物は、導体層と前記導体層と接する導電性物質層を有する研磨対象物を研磨する用途で使用される研磨用組成物である。研磨対象物は、具体的には、半導体デバイスの配線部形成工程における、表面が凹部および凸部からなる層間絶縁膜と、前記層間絶縁膜を表面に沿って被覆するバリア導体層と、前記凹部を充填してバリア導体層を被覆する銅を主成分とする導電性物質層とを有する基板が挙げられる。
Z8703に規定される常温をいい、pHは研磨用組成物のpHに依存する。なお、ここでいう電流値は、小数点以下第4位の値を四捨五入した値を用いる。
研磨用組成物には、任意で酸化剤を含有させることができる。酸化剤は研磨対象物の表面を酸化する作用を有し、研磨用組成物中に酸化剤を加えた場合には、研磨用組成物による研磨速度が向上する効果がある。
研磨用組成物には、任意で砥粒を含有させることができる。砥粒は、無機粒子、有機粒子、及び有機無機複合粒子のいずれであってもよい。無機粒子の具体例としては、例えば、シリカ、アルミナ、セリア、チタニアなどの金属酸化物からなる粒子、並びに窒化ケイ素粒子、炭化ケイ素粒子及び窒化ホウ素粒子が挙げられる。有機粒子の具体例としては、例えばポリメタクリル酸メチル(PMMA)粒子が挙げられる。その中でもシリカ粒子が好ましく、特に好ましいのはコロイダルシリカである。
研磨用組成物は、任意で研磨促進剤を含有させることができる。研磨用組成物中に含まれる錯化剤は、研磨対象物の表面を化学的にエッチングする作用を有し、研磨用組成物による研磨速度を向上させる働きをする。
研磨用組成物は、任意で金属防食剤を含有させることができる。研磨用組成物中に金属防食剤を加えた場合には、研磨用組成物を用いて研磨した後の研磨対象物の表面にディッシング等の表面欠陥がより生じにくくなる効果がある。また、その金属防食剤は、研磨用組成物中に酸化剤及び/又は錯化剤が含まれている場合には、酸化剤による研磨対象物の表面の酸化を緩和するとともに、酸化剤による研磨対象物の表面の金属の酸化により生じる金属イオンと反応して不溶性の錯体を生成する働きをする。その結果、錯化剤による研磨対象物の表面へのエッチングを抑制することができ、研磨後の研磨対象物の平滑性が向上する。
研磨用組成物のpHの上限は特に限定されないが、12であることが好ましく、より好ましくは11、さらに好ましくは10である。研磨用組成物のpHが小さくなるにつれて、 研磨対象物の表面の過剰なエッチング抑制の効果があり、その結果として過剰な研磨及び腐食を抑制する効果を得ることができる。
本実施形態の研磨用組成物は導体層と前記導体層と接する導電性物質層を有する研磨対象物を研磨する用途で使用される研磨用組成物であって、前記研磨用組成物中において電位計の正極側を前記導電性物質に接続し、負極側を前記導体に接続した場合の室温で、導電性物質(正極)と導体(負極)両面の研磨中において正極側から負極側へ流れる電流の値が、正の値(ゼロを含む。)を示す。この研磨用組成物により、導体へ導電性物質からの電子の移動を、すなわち、導体から導電性物質への電流が流れを防止することができ、導体と導電性物質との境界部近傍の導電性物質表面から電子と導電性物質イオンの研磨用組成物中への溶出を防止することができる。その結果、腐食欠陥を防止することができると考えられる。
・ 前記実施形態の研磨用組成物は、必要に応じて、界面活性剤や水溶性高分子、防腐剤のような公知の添加剤をさらに含有してもよい。この場合、公知の添加剤について制限はなく、結果として、完成した研磨用組成物が特定の条件下で研磨用組成物中において電位計の正極側を前記導電性物質に接続し、負極側を前記導体に接続した場合の正極側から負極側へ流れる電流の値が、正の値(ゼロを含む。)を示せばよい。
・ 前記実施形態の研磨用組成物は一液型であってもよいし、二液型を始めとする多液型であってもよい。
・ 前記実施形態の研磨用組成物は、研磨用組成物の原液を水で希釈することにより調製されてもよい。
表1〜3に記載の組成となるように各成分を混合することにより、実施例1〜26及び比較例1〜78の研磨用組成物を調整した。表1〜3の“砥粒”欄の“含有量(質量%)”欄には、各研磨用組成物中の砥粒の含有量を示す。ここでの砥粒は、約70nmの平均二次粒子径(平均一次粒子径35nm、平均会合度2)を有するコロイダルシリカを使用した。表1〜3の“導体と導電性物質との間に流れる電流値を正の値にする添加剤”欄の“種類”欄には、実施例又は比較例において各研磨用組成物中に含まれる導体及び導電性物質との間に流れる電流値を正の値にする添加剤の種類を示す。また、“含有量(質量%)”欄には、各研磨用組成物中の導体と導電性物質との間に流れる電流値を正の値にする添加剤の含有量を示す。表1〜3の“pH”欄には、各研磨用組成物中のpHを示す。なお、pHは無機酸又は無機塩基を添加して所定の値に調整した。また、各研磨用組成物は、研磨直前に過酸化水素を2質量%になるように添加した。
Claims (7)
- 導体層と前記導体層と接する導電性物質層を有する研磨対象物を研磨する用途で使用される研磨用組成物であって、
常温の前記研磨用組成物中で電位計の正極側を前記導電性物質に接続し、且つ負極側を前記導体に接続した条件において、前記導電性物質と前記導体を研磨したときに正極側から負極側へ流れる電流の値が、正の値(ゼロを含む。)を示すことを特徴とする研磨用組成物。 - 前記導体及び前記導電性物質との間に流れる電流値を正の値(ゼロを含む。)にする添加剤を含有する、請求項1に記載の研磨用組成物。
- 前記電流値を正の値(ゼロを含む。)にする添加剤が、窒素原子含有化合物、硫黄原子含有化合物及びリン原子含有化合物からから選ばれるいずれか一以上である、請求項1又は2に記載の研磨用組成物。
- 前記導体が、貴金属を含む、請求項1〜3のいずれか一項に記載の研磨用組成物。
- 前記導体が、ルテニウムを含む、請求項1〜4のいずれか一項に記載の研磨用組成物。
- 請求項1〜5のいずれか一項に記載の研磨用組成物を用いて、導体層と前記導体層と接する導電性物質層を有する研磨対象物の表面を研磨することを含む研磨方法。
- 請求項6に記載の研磨用組成物を用いて、導体層と前記導体層と接する導電性物質層を有する基板を得るべく、導体層と前記導体層と接する導電性物質層を有する研磨対象物の表面を研磨して導体層と前記導体層と接する導電性物質層の一部を除去することを含む、導体層と前記導体層と接する導電性物質層を有する基板の製造方法。
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