JP2005097736A - 銅を覆う障壁物質を形成するための半導体処理方法及び組成物 - Google Patents
銅を覆う障壁物質を形成するための半導体処理方法及び組成物 Download PDFInfo
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- 230000004888 barrier function Effects 0.000 title claims abstract description 68
- 239000004065 semiconductor Substances 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 44
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- 238000009792 diffusion process Methods 0.000 claims description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 33
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- 239000010937 tungsten Substances 0.000 claims description 33
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
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- 229910052796 boron Inorganic materials 0.000 claims description 24
- 239000003002 pH adjusting agent Substances 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 9
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 9
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- -1 citric acid compound Chemical class 0.000 claims description 4
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- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003381 stabilizer Substances 0.000 abstract description 3
- CPJYFACXEHYLFS-UHFFFAOYSA-N [B].[W].[Co] Chemical compound [B].[W].[Co] CPJYFACXEHYLFS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000080 wetting agent Substances 0.000 abstract description 2
- 239000003989 dielectric material Substances 0.000 abstract 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- 230000000694 effects Effects 0.000 description 9
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- 150000001868 cobalt Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical group [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004803 Na2 WO4.2H2 O Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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Abstract
【解決手段】low k絶縁物質とのより優れた適合を可能にする、高い熱的安定度及び範囲を備えたモルホリンボランめっき浴を使用する。仮に溶液に溶解した銅のような原料物質があればそれを錯体にするために、金属源と共に異なった安定度定数を備えたキレート剤の混合物を使用する。フルオロ界面活性剤を潤湿剤及び安定剤として使用する。
【選択図】 なし
Description
本発明は、半導体及び集積回路装置のような装置における膜の形成(例えば、析出)、より詳細には、半導体装置における拡散障壁膜に関するものである。
リンゴ酸、TMAH、タングステン酸のような化合物を含めることができるであろう。
その処理方法のなお別のさらなる実施形態において、ニッケルもしくはコバルトを含んだ物質にはさらにコバルト塩化物及びコバルト硫酸塩のうち一方が含まれている。
Claims (10)
- 無電解めっき浴槽を用意し、
ニッケル及びコバルトのうち少なくとも一方を含む溶液を形成するために、水中にニッケルもしくはコバルトを含む物質を溶解し、
第一安定度定数を備えた第一キレート剤をその溶液に添加し、
その第一キレート剤と同様に溶液中に浮遊するニッケル及びコバルトのうち少なくとも一方を保持するように機能し、第一安定度定数とは異なる第二安定度定数を備えた第二キレート剤をその溶液に添加し、
緩衝剤として機能し、異なったpH値を伴う、異なった組成を備えた第一及び第二pH調整剤を前記溶液のpHを増加させるためにその溶液に添加し、
その溶液に拡散障壁物質を添加し、
めっきの均一性を高め、かつ前記溶液を化学的に安定化させるために、その溶液に少なくとも一つの界面活性剤を添加し、
ニッケルもしくはコバルトを含む物質のニッケル及びコバルトのうち少なくとも一方を固体に変化させるためにその溶液にホウ素を含む物質を添加し、
予め定められた温度までその溶液を加熱し、
無電解めっき浴槽中に露出金属を備えた半導体装置を配置し、
露出金属を覆うとともに、ホウ素、拡散障壁物質並びにニッケル及びコバルトのうち少なくとも一方の組み合せを含む障壁膜を形成するようにその半導体装置をめっきし、
その溶液からその半導体装置を取り外すことを含んだ半導体処理方法。 - 前記第一キレート剤としてクエン酸化合物を添加し、
前記第一キレート剤としてクエン酸ナトリウムを添加し、
溶液を安定化し、かつ好ましくはいかなる溶解金属をもキレートとするための前記第二キレート剤としてリンゴ酸、酒石酸、グリシン及びシュウ酸のうちの一つを添加し、
前記拡散障壁物質としてタングステン、クロム、モリブデン、レニウム及びジルコニウムを使用し、
前記露出金属として銅を使用することをさらに含む請求項1の処理方法。 - 第一界面活性剤とその第一界面活性剤とは異なる安定度パラメータを備えた第二界面活性剤とを添加することをさらに含む請求項1の処理方法。
- 半導体処理方法における、銅上の拡散障壁物質の膜の無電解めっきのための処理組成物であって、その組成物は、
コバルトを含む化合物と、
コバルトを選択的にキレートするための第一キレート剤と、
その組成物中のいかなる溶解金属をも選択的にキレートする第一キレート剤とは異なる第二キレート剤と、
その組成物を緩衝し、かつ予め定められた量だけその組成物のpHを調整するための第一pH調整剤と、
第一金属源を提供するためのタングステンを含む化合物と、
拡散障壁物質の膜におけるタングステン析出量を増加させる第一表面張力低下特性を備えた第一界面活性剤と、
拡散障壁物質の膜における析出の均一性を向上させる第二表面張力低下特性を備えた第二界面活性剤とを含む処理方法。 - 前記コバルトを含む化合物は硫酸コバルト七水和物を含み、かつ化合物1リットルあたり約27から35グラムであり、
前記第一キレート剤は化合物1リットルあたり約27から35グラムのクエン酸三ナトリウムもしくは1リットルあたり約25から30グラムのクエン酸の一方を含み、
前記第二キレート剤はリンゴ酸を含み、化合物1リットルあたり約27から35グラムであり、
前記第一pH調整剤はテトラメチルアンモニウム水酸化物(TMAH)を含み、かつ化合物の約1.0から1.5パーセントを占め、
前記第二pH調整剤は予め定められたpHにその組成物のpHを至らせるのに必要なだけの量の水酸化カリウムを含み、
前記タングステンを含む化合物は化合物1リットルあたり約8から12グラムのタングステン酸ナトリウム二水和物もしくは化合物1リットルあたり約6から10グラムのタングステン酸の一方を含み、
前記第一界面活性剤は化合物の約15から40ppm(パーツ パー ミリオン)を占め、
前記第二界面活性剤は化合物の約20から100ppmを占める請求項4の処理方法。 - 前記第一キレート剤はクエン酸化合物を含み、かつ前記第二キレート剤はリンゴ酸、酒石酸、グリシン及びシュウ酸のうちの一つを含む請求項4の処理方法。
- 前記化合物は、組成物をさらに緩衝し、かつ予め定められたpHにその組成物のpHをさらに調整するための第二pH調整剤をさらに含んでいる請求項4の処理方法。
- 銅上の拡散障壁物質の膜の無電解めっきにおいて使用するための半導体処理溶液であって、その半導体処理溶液は、
金属を含む化合物と、
その金属を選択的にキレートするための第一キレート剤と、
組成物中の他のいかなる金属をも選択的にキレートする第一キレート剤とは異なる第二キレート剤と、
組成物を緩衝し、かつその組成物のpHを予め定められた量だけ調整するための第一pH調整剤と、
第一金属源を提供するタングステンを含む化合物と、
拡散障壁物質の膜におけるタングステン析出量を増加させる第一表面張力低下特性を備えた第一界面活性剤と、
拡散障壁物質の膜における析出の均一性を向上させる第二表面張力低下特性を備えた第二界面活性剤とを含む半導体処理溶液。 - 前記金属はコバルト及びニッケルのうち少なくとも一方をさらに含んでいる請求項8の半導体処理溶液。
- ホウ素を含んだ化合物をさらに含む請求項8の半導体処理溶液。
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