Improved copper bath for electroplating fine circuitry on...

C - Chemistry – Metallurgy – 25 – D

Patent

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C25D 3/38 (2006.01) H01L 21/768 (2006.01)

Patent

CA 2539481

Bottom-up filling of fine Damascene trenches and vias in semiconductor chips is attained using a copper pyrophosphate electroplating bath with a single accelerating additive species present at low concentration (< 5 ~M). This bath is much easier to control than the acid copper sulfate bath, which employs a complicated additive system involving a minimum of two organic additives and chloride ion (as well as significant additive breakdown products). Pyrophosphate copper deposits exhibit stable properties without annealing and are typically twice as hard as acid sulfate copper deposits, which facilitates chemical mechanical planarization. The mechanical properties and texture of the fine-grained pyrophosphate copper deposits are also much less substrate dependent, which minimizes the effects of variations and flaws in the barrier and seed layers. Attack of copper seed layers is minimized for the copper pyrophosphate bath, which operates in the pH 8 to 9 range. The resistivity of pyrophosphate and annealed acid sulfate copper deposits are substantially equivalent.

L'invention concerne le remplissage de bas en haut de fines tranchées et traversées en damasquinage sur puces à semi-conducteurs, par bain de galvanoplastie au pyrophosphate de cuivre, avec présence d'espèce additive d'accélération unique en faible concentration (< 5 ?<U>M</U>). On contrôle bien plus facilement ce bain que le bain de sulfate de cuivre acide, qui fait appel à un système additif complexe faisant intervenir un minimum de deux additifs organiques et d'ion chlorure (et des produits de dégradation additifs importants). Les dépôts de cuivre de pyrophosphate ont des propriétés stables sans recuit et ils sont généralement deux fois plus durs que les dépôts de sulfate de cuivre acide, ce qui facilite la planarisation chimique mécanique. Les propriétés mécaniques et la texture des dépôts de pyrophosphate de cuivre à grain fin sont également bien moins dépendants du substrat, ce qui réduit au minimum les effets des variations et des défauts dans les couches barrière et semence. On réduit au minimum l'attaque des couches semence de cuivre pour le bain de pyrophosphate de cuivre, pour lequel le pH est compris entre 8 et 9. La résistivité des dépôts de pyrophosphate et de sulfate de cuivre recuit est sensiblement équivalente.

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