JP5412517B2 - バリア層除去方法及び装置 - Google Patents
バリア層除去方法及び装置 Download PDFInfo
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- JP5412517B2 JP5412517B2 JP2011523289A JP2011523289A JP5412517B2 JP 5412517 B2 JP5412517 B2 JP 5412517B2 JP 2011523289 A JP2011523289 A JP 2011523289A JP 2011523289 A JP2011523289 A JP 2011523289A JP 5412517 B2 JP5412517 B2 JP 5412517B2
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- barrier layer
- tantalum oxide
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- 230000004888 barrier function Effects 0.000 title description 56
- 238000000034 method Methods 0.000 title description 43
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 55
- 229910001936 tantalum oxide Inorganic materials 0.000 description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 43
- 229910052802 copper Inorganic materials 0.000 description 43
- 239000010949 copper Substances 0.000 description 43
- 239000010408 film Substances 0.000 description 37
- 238000005530 etching Methods 0.000 description 34
- 230000008569 process Effects 0.000 description 32
- 239000007789 gas Substances 0.000 description 21
- 239000004065 semiconductor Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 15
- 238000005498 polishing Methods 0.000 description 15
- 229910052715 tantalum Inorganic materials 0.000 description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 12
- 239000003989 dielectric material Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001020 plasma etching Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- -1 TaO Chemical class 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
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- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
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- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
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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
- 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
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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
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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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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
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- Chemical Kinetics & Catalysis (AREA)
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
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Description
2Ta+5H2O=Ta2O5+10H++10e−
銅電解研磨工程の電極における水のため、銅研磨の後では、酸化タンタルはほとんど五酸化タンタルである。五酸化タンタルはかなり高い化学安定性を有する。それは銅研磨の間にバリア層の保護として機能するが、次の段階ではバリア層を除去することがより難しくなる。XeF2ガスは適切な速度でTa及びTaN203をエッチングするが、酸化タンタル205をエッチングすることは困難であり、所定条件では全くエッチングできない。酸化タンタル205はマスク層として機能し、Ta及びTaN203がXeF2ガスによってエッチングされることを防ぐ。非常に長い間XeF2はTa及びTaN層の部分を除去するが、図7に示すようにピンホールの原因となる。図7は、銅204がSFPにて研磨された後に、酸化タンタルフィルム205除去工程無しで、バリア層Ta及びTaN203がXeF2によってエッチングされることを示す。所定時間XeF2によってエッチングされた後、ピンホール領域の周りを除いてバリア層203は除去されていないように見える。バリアを効率的且つ一様に除去するために、バリア層203の上の酸化タンタルフィルム205は最初に除去されるべきである。
Ta2O5+14F−+10H+=2TaF7 2−+5H2O
HF/BHFの濃度は0.1w%〜30w%であり、0.5%〜4%が好ましい。処理温度は0℃〜50℃であり、室温が好ましい。処理時間はHF/BHFの濃度及び温度に依存する。ここで溶液は酸化タンタルフィルム205及びバリア層タンタル203の部分をエッチングし、銅層204に損傷を与える原因とならない。しかし処理が非常に強い、エッチング時間が非常に長い、又はエッチング濃度が非常に高い場合は、バリア層Ta/TaN203は除去される。図8は、エッチング液が非常に強い場合に、パッド側壁のバリアTa/TaN203が損傷することを示す。側壁のバリア層の少なくとも一部が損傷していることが明らかに見られる。そのため溶液により低k誘電層202が損傷を受ける。適切な処理は酸化タンタルフィルム205をエッチングすることである。図9に示されるように、酸化タンタルフィルム205がエッチングされた後、残存するバリア層Ta/TaN203は、XeF2によって図7に示されるものと比較して効率的に除去される。
Claims (16)
- 基板、誘電層、前記誘電層上のバリア層、及び前記バリア層上の金属層を有し、前記金属層が充填されているパターンを有する半導体構造体の処理方法であって、
無応力電解研磨(SFP)により前記バリア層の上の前記金属層を除去し、
無応力電解研磨の間に形成された前記バリア層の酸化タンタル又は酸化チタンフィルムを除去し、
XeF2ガスを用いて前記バリア層を除去し、構造体のパターンを完全に離隔し、
前記バリア層の酸化タンタル又は酸化チタンフィルムの少なくとも一部が、前記金属層の無応力電解研磨の間に形成され、
前記バリア層の酸化タンタル又は酸化チタンが、HF又はBHFを含む溶液であるエッチング試薬により除去されることを特徴とする半導体構造体の処理方法。 - 前記バリア層は、タンタル若しくはチタンの純組成又は化合物からなる群から選択されることを特徴とする請求項1に記載の方法。
- 前記金属層が銅層であることを特徴とする請求項1に記載の方法。
- 前記誘電層が、1.2よりも大きく4.2未満である誘電定数を有する誘電材料で形成されていることを特徴とする請求項1に記載の方法。
- 前記バリア層の酸化タンタル又は酸化チタンフィルムが、KOH又はNaOHであるエッチング試薬により除去され、
前記溶液の濃度は0.1wt%〜50wt%であり、
温度は0℃〜90℃であることを特徴とする請求項1に記載の方法。 - 前記バリア層の酸化タンタル又は酸化チタンフィルムが、クエン酸、シュウ酸、又はこれらの混合物により除去され、
試薬の濃度は0.1wt%〜10wt%であり、
温度は0℃〜80℃であることを特徴とする請求項1に記載の方法。 - 前記XeF2ガスの圧力が、0.1Torr〜100Torrであることを特徴とする請求項1に記載の方法。
- 前記基板の温度が0℃〜300℃であることを特徴とする請求項7に記載の方法。
- 基板、誘電層、前記誘電層上のバリア層、及び前記バリア層上の金属層を有し、前記金属層が充填されているパターンを有する半導体構造体を製造する装置であって、前記装置は、
前記バリア層の上の前記金属層を除去する無応力電解研磨系と、
無応力電解研磨の間に形成された前記バリア層の酸化タンタル又は酸化チタンフィルムを除去する、酸化タンタル又は酸化チタンフィルム除去系と、
構造体のパターンを完全に離隔するために前記バリア層を除去するエッチング系と、を備え、
前記酸化タンタル又は酸化チタンフィルム除去系は、
酸化タンタル又は酸化チタンフィルムを除去するためにHF又はBHFを含む溶液であるエッチング試薬を使用することを特徴とする装置。 - 前記バリア層は、タンタル若しくはチタンの純組成又は化合物からなる群から選択されることを特徴とする請求項9に記載の装置。
- 前記酸化タンタル又は酸化チタンフィルム除去系は、酸化タンタル又は酸化チタンフィルムを除去するためにKOH又はNaOHであるエッチング試薬を使用し、
前記溶液の濃度は0.1wt%〜50wt%であり、
温度は0℃〜90℃であることを特徴とする請求項9に記載の装置。 - 前記酸化タンタル又は酸化チタンフィルム除去系が、酸化タンタル又は酸化チタンフィルムを除去するためにCF4/O2プラズマを使用することを特徴とする請求項9に記載の装置。
- 前記酸化タンタル又は酸化チタンフィルム除去系が、酸化タンタル又は酸化チタンフィルムを除去するために、Ar、He、Ne、Xe、及びKrからなる群から選択される不活性ガスを使用してなされるイオンスパッタリングを使用することを特徴とする請求項9に記載の装置。
- 前記酸化タンタル又は酸化チタンフィルム除去系が、前記バリア層の酸化タンタル又は酸化チタンフィルムを除去するために、クエン酸、シュウ酸、又はこれらの混合物を使用し、
試薬の濃度は0.1wt%〜10wt%であり、
温度は0℃〜80℃であることを特徴とする請求項9に記載の装置。 - バリア層エッチング系が、バリア層のTa/TaN又はTi/TiNを除去するためにXeF2ガスを使用し、
前記XeF2ガスの圧力が0.1Torr〜100Torrであることを特徴とする請求項9に記載の装置。 - 前記基板の温度が0℃〜300℃であることを特徴とする請求項15に記載の装置。
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- 2008-08-20 WO PCT/CN2008/072059 patent/WO2010020092A1/en active Application Filing
- 2008-08-20 JP JP2011523289A patent/JP5412517B2/ja not_active Expired - Fee Related
- 2008-08-20 US US13/059,814 patent/US8598039B2/en active Active
- 2008-08-20 KR KR1020117006278A patent/KR101492467B1/ko not_active Expired - Fee Related
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2013
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JP2012500480A (ja) | 2012-01-05 |
US8598039B2 (en) | 2013-12-03 |
KR101492467B1 (ko) | 2015-02-11 |
KR20110051251A (ko) | 2011-05-17 |
US20140053978A1 (en) | 2014-02-27 |
US20110177692A1 (en) | 2011-07-21 |
WO2010020092A1 (en) | 2010-02-25 |
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