JP5074025B2 - 半導体工業に使用するための三成分系材料を無電解メッキする組成物 - Google Patents
半導体工業に使用するための三成分系材料を無電解メッキする組成物 Download PDFInfo
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- JP5074025B2 JP5074025B2 JP2006505229A JP2006505229A JP5074025B2 JP 5074025 B2 JP5074025 B2 JP 5074025B2 JP 2006505229 A JP2006505229 A JP 2006505229A JP 2006505229 A JP2006505229 A JP 2006505229A JP 5074025 B2 JP5074025 B2 JP 5074025B2
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 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
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
超小型電子構造素子の上昇する配線密度および速度要件は、銅上での従来のアルミニウム(合金)の導電路配線材料の材料交換を生じさせた。銅を使用することによって、よりいっそう低い電気抵抗およびよりいっそう高い安定性がエレクトロマイグレーションの際に達成され、それによって配線密度が増加することにより生じる、導体路の上昇する全抵抗率が計算される。
米国特許第4019910号明細書には、ニッケル含有の三成分系合金をメッキさせるための混合物および製出方法が記載されている。米国特許第5695810号明細書には、半導体工業で使用するためのCoW−P金属バリヤー層を無電解メッキさせるための方法の特許保護が請求されている。更に、米国特許第2002/0098681号明細書A1には、三成分系拡散バリヤーの無電解メッキおよび新規の銅配線を備えた集積回路のエレクトロマイグレーションに対する安定性を改善するためのCoW−B、CoMo−B、CoW−P、CoSn−Pからなるケーシング層が記載されている。
従って、本発明の課題は、導電性構造体を無電解メッキするための組成物ならびに清浄化工程および活性化工程を含めて前記構造体を製造するための方法を提供することであり、それによって、簡単で安価な方法で接触活性化を行なった後に誘電体(例えば、SiO2、SiOC、SiN、SiC)上にメッキすることができるかまたは直接に銅配線上にメッキすることができ、実際に配線材料として施こされた銅の拡散を阻止するためにバリヤー層として使用される構造体をメッキすることができる。
銅配線表面を清浄化(脱酸化)し、場合によっては引続き配線表面を活性化する工程、ならびに
予め完成された自動接触電気メッキ溶液を準備する工程および
次に既に予め完成された化学的電気メッキ溶液で支持体を噴霧または浸漬する工程を含む。
新規に配合された水性組成物は、組み合わされた拡散バリヤー層と核形成層とを無電解メッキするために使用されてよい。最後に、本発明による組成物を使用する場合には、唯一の処理工程で行なうことができる。しかし、この組成物は、ケーシング化材料をCu配線上にメッキするために使用されてもよい。
好ましい濃度範囲は、次の表中に記載されている。
NiMo−Pに関連して、実施例の溶液は、9のpH値を有し、この場合には、このpH値の±1以下で偏倚している。それというのも、さもないと、変化されたバリヤー特性を有する変化された合金組成が生じるからである。
本発明によれば、先行する清浄化工程および活性化工程により導電性構造体を製造する方法が提供される。清浄化の順序は、場合によっては清浄化作用を改善するためにアルコール洗浄、例えばエタノール、イソプロピルアルコールによって拡大させることができる。清浄化は、機械的なブラッシング処理(”スクラバー”)を使用することによって補助されてもよい。
本発明によれば、延長された可使時間を有する無電解メッキ浴のための組成物が提供される。本発明によれば、改善された性質は、前記したような適当な添加剤を添加することによって達成される。この可使時間の延長は、僅かな化学薬品の消費量を引き起こし、付加的に製造工程の場合に作業費用は、減少し、それによって得られた製品の費用も減少する。また、この添加剤の添加によって、不変の単一の層成長が促進され、アスペクト比が増加するにつれて、組み込まれた構造素子中での導体路およびコンタクト孔の寸法が減少される。
前記層の深部形状(Tiefenprofile)は、ニッケルが一様に深部の機能層としてメッキされ、一方で、燐は、上部の表面層に向かって含量が増加し、および高融点金属は、切断個所バリヤー/SiO2に向かって含量が増加する傾向にある。種々の合金のニッケル、燐および高融点金属成分の標準化された原子画分が示される。ニッケル画分は、約60〜70原子%で比較的一定のままであり、一方で、残留成分、特に燐については、大きな変動が測定される。この場合に設定された全ての三成分系合金は、例えばNiMo−P薄膜については23原子%までの高融点金属の高い含量を含有する(第3表)。
Cuが嵌め込まれた構造体上での金属バリヤーとしての開発された三成分系の合金の使用に関連して、数多くの問題が評価されなければならなかった。重要な視点は、Cu構造体上での完全に選択的なメッキである。試験されたニッケルをベースとした合金は、切断個所Cu/自己配向されたバリヤーの相分離を回避させるために好ましい材料である。それというのも、Niは、CUとの強力な共有結合を形成させる傾向を有し、このことは、境界層の付着力に対して有利に作用する。付加的に、Cu表面を準備することおよび無電解での金属メッキ浴の安定性は、重大な問題を生じる。それというのも、この金属メッキ浴は、準安定性の熱力学的平衡で存在しかつ自然発生的に分解する傾向にあるからである。従って、Cu表面の準備は、前記の接触的処理工程の場合に重要な役を演じる。無電解での合金のメッキ前に、酸化銅の除去を含む湿式工程がCMPおよびPd触媒の活性化の後に展開された。最初に、酸による清浄化は、有機酸を含有する後CMP清浄化溶液を使用しながら実施され、選択的に酸化銅が除去された。直ぐ次の工程で、Cu表面は、非連続的なPd種晶形成層をメッキすることによって活性化され、このことは、次亜燐酸塩を含有する金属メッキ溶液の使用によって三成分系合金の無電解メッキを可能にした(図2)。
工程1(清浄化):
付着する酸化銅および有機銅化合物の銅表面を清浄化するためには、後銅CMP清浄化混合物が使用され、例えばMerck社のCuPureTMInoclean200が使用される。マロン酸ジメチルエステル2〜4%、1−メトキシ−2−プロパノール2〜4%、酢酸メチルエステル0.5%未満および燐酸0.5%未満からなる。この場合、清浄化溶液は、80%の溶液として、ならびに希釈時に10%までの溶液として浸漬法ならびに噴霧法で使用されることができる。場合によっては、清浄化のために、エタノールまたはイソプロパノールを用いて他の浸漬(Dip)工程を行なうことができる。アルコールは、処理工程の節約のために直接に清浄化混合物に添加されてよい。
清浄化溶液Inoclean200(希釈率10%)中での2分間の浸漬時間、DI水での30秒間の洗浄、および乾燥吹込なし。
こうして清浄化されたCu表面をPd2+含有溶液での処理によって電気化学的な電荷交換により選択的に活性化される。
a.)酢酸5.0モル/l
PdCl2、1×10−3モル/l
HCl(37%)、1×10−4モル/l
b.)酢酸5.0モル/l
Pd(OAc)2、1×10−3モル/l
HCl(37%)、1×10−3モル/l。
NiM−Rの清浄化工程、活性化工程およびメッキ工程は、連続的に極めて僅かな時間間隔で行なわれる。
更に、Pd種晶で活性化されたCu配線表面上に三成分系の金属合金、例えばNiMo−Pがメッキされる。
NiSO4×6H2O 26.29g/l (0.1モル/l)、
Na3クエン酸塩×2H2O 26.47g/l (0.09モル/l)、
Na2MoO4×2H2O 0.24g/l (0.001モル/l)、
コハク酸 23.62g/l (0.2モル/l)、
NaH2PO2×H2O 21.20g/l 0.2モル/l。
原液K1=NiSO4×6H2O 131.5g/l、
原液K2=Na3クエン酸塩×2H2O 132.4g/l、
原液K3=Na2MoO4×2H2O 1,2g/l(基本電解質1参照)、
原液K4=コハク酸 118.1g/l、
原液K5=NaH2PO2×H2O 106.0g/l。
NiSO4×6H2O 26.29g/l 0.1モル/l、
Na3クエン酸塩×2H2O 26.47g/l 0.09モル/l、
Na2MoO4×2H2O 0.24g/l 0.001モル/l、
コハク酸 1.18g/l 0.01モル/l、
NaH2PO2×H2O 21.20g/l 0.2モル/l。
NiSO4×6H2O 26.29g/l (0.1モル/l)、
Na3クエン酸塩×2H2O 26.47g/l (0.09モル/l)、
Na2MoO4×2H2O 0.24g/l (0.001モル/l)、
コハク酸 1.18g/l (0.01モル/l)、
NaH2PO2×H2O 31.8g/l 0.2モル/l。
NiSO4×6H2O 26.29g/l (0.1モル/l)、
Na3クエン酸塩×2H2O 26.47g/l (0.09モル/l)、
Na2MoO4×2H2O 0.24g/l (0.001モル/l)、
コハク酸 23.62g/l (0.2モル/l)、
NaH2PO2×H2O 21.20g/l 0.2モル/l。
全ての基本電解質1〜4には、添加剤が添加されてもよい。このために、
ジチオジグリコール酸3.75ppm、
Brij 58 75ppm
を選択的に個々にかまたは組み合わせて9.0へのpH値の調節前に添加する。
支持体を清浄化およびPdの活性化を行なった後に、電気メッキによるメッキ溶液中に浸漬する(溶液を攪拌する)。混合物を55℃に温度調節する。2分間、自動接触メッキを行なう。NiMo−P合金がPd種晶上にメッキされると直ちに、この合金は、金属光沢を有する層によって目視可能になる。合金メッキ後に、DI水で洗浄し、注記深く窒素ガスで乾式吹き付けを行なう。
工程1 例1と同様の清浄化。
金属合金(NiMo−P)を銅表面上に直接に無電解メッキさせるために、この場合には、Pd触媒種晶による活性化を行なわない。その代わりに、NiMo−P溶液を開始剤としてのDMABの添加によって変性し、無電解メッキのために使用する。試験を実施するために、0.004〜0.15モル/lの範囲内の種々のボラン濃度を使用する。
ジメチルアミノボラン=0.004モル/lおよび0.012モル/l
と一緒に記載される。
原液K1=NiSO4×6H2O 131.5g/l、
原液K2=Na3クエン酸塩×2H2O 132.4g/l、
原液K3=Na2MoO4×2H2O 1,2g/l(基本電解質1参照)、
原液K4=コハク酸 118.1g/l、
原液”K5−1”=NaH2PO2×H2O 106.0g/l+ジメチルアミノボラン 5.88g/l。
原液”K5−2”=NaH2PO2×H2O 106.0g/l+ジメチルアミノボラン 17.69g/l。
前記支持体を30秒間清浄化を行なった後にDI水で洗浄する。引続き、付加的な清浄化工程をエタノール中で行なう。DI水中で10秒間洗浄し、引続き電気メッキによるメッキ溶液中に浸漬する(溶液を攪拌する)。メッキを30秒間K5−1の混合物を用いて60℃で行ない、K5−2を用いて50℃で行なう。NiMo−P合金がPd種晶上にメッキされると直ちに、自動接触メッキが行なわれ、金属光沢層によって目視可能になる。合金のメッキ後に、DI水で洗浄し、注記深く窒素ガスで乾式吹き付けを行なう。
種々の絶縁材料と比較したPd活性化溶液を用いての選択的なメッキの測定
種々の絶縁材料と比較した直接的な自動接触電気メッキによる選択的なメッキの測定
Claims (12)
- 導電性構造体をケーシング化バリヤー層として形成させる方法において、
無電解メッキ法により、NiSO 4 ×6H 2 O、NaH 2 PO 2 、およびNa 2 MoO 4 またはKReO 4 の化合物、場合によっては他の添加剤を適当な濃度で含有する水溶液を用いて、金属支持体表面上に、NiRe−P合金、NiMo−P合金、NiRe−B合金またはNiMo−B合金からなるケーシング化バリヤー層を形成し、
この場合この金属支持体は、Cu、Ag、Co、Ni、PdおよびPtの群から選択された1つの金属からなり、
高融点金属としてバリヤー層中にモリブデンが3〜24原子%の量で含有されているかまたはレニウムが2〜23原子%の量で含有されており、
前記水溶液中でのNa 2 MoO 4 の濃度は、最大3×10 -2 mol/lであり、および前記水溶液中でのKReO 4 の濃度は、最大1×10 -2 mol/lであることを特徴とする、導電性構造体をケーシング化バリヤー層として形成させる方法。 - 金属支持体は、銅配線から選択される、請求項1記載の方法。
- NiRe−P合金またはNiMo−P合金をケーシング化バリヤー層として使用する、請求項1記載の方法。
- 前記水溶液として、本質的に界面活性剤を含有しない溶液を使用する、請求項1から3までのいずれか1項に記載の方法。
- 前記水溶液として、少なくとも1つのアニオン界面活性剤または非イオン界面活性剤を含有する溶液を使用する、請求項1から3までのいずれか1項に記載の方法。
- 前記水溶液として、メッキ溶液の浴可使時間を延長するための安定剤を含有する溶液を使用する、請求項1から5までのいずれか1項に記載の方法。
- 前記金属支持体表面を清浄化および活性化するために、前記水溶液として、アンモニアおよびフッ化水素酸を含有しない溶液を使用する、請求項1から6までのいずれか1項に記載の方法。
- 前記活性化をPd触媒で行なう、請求項7に記載の方法。
- 前記水溶液中でのNiSO 4 ×6H 2 Oの濃度は、Na 2 MoO 4 の場合に0.02〜0.1mol/lであり、KReO 4 の場合には、0.03〜0.1mol/lである、請求項1から8までのいずれか1項に記載の方法。
- 前記水溶液中でのNaH 2 PO 2 の濃度は、Na 2 MoO 4 の場合に0.1〜0.5mol/lであり、KReO 4 の場合には、0.2〜0.8mol/lである、請求項1から9までのいずれか1項に記載の方法。
- 前記水溶液は、4.5〜9.0の範囲内のpH値を有する、請求項1から10までのいずれか1項に記載の方法。
- 前記水溶液は、Na 3 C 6 H 5 O 7 ×2H 2 O、C 4 H 6 O 4 、Na 2 C 4 H 4 O 4 ×6H 2 O、2,2−ビピリジン、チオ二酢酸、ポリオキシエチレンオクチルフェニルエーテル、ジメチルアミノボラン、Na 2 C 2 H 3 O 2 、C 3 H 6 O 3 (90%)、(NH 4 ) 2 SO 4 およびナトリウム−ポリ(オキシエチレン)−フェニルエーテルホスフェートの群から選択された添加剤を含有する、請求項1から11までのいずれか1項に記載の方法。
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