Chemical mechanical polishing pad
The present invention provides methods of CMP polishing a metal surface, such as a copper or tungsten containing metal surface in a semiconductor wafer, the methods comprising CMP polishing the substrate with a CMP polishing pad that has a top polishing surface in a polishing layer which is the reaction product of an isocyanate terminated urethane prepolymer and a curative component comprising a polyol curative having a number average molecular weight of 6000 to 15,000, and having an average of 5 to 7 hydroxyl groups per molecule and a polyfunctional aromatic amine curative, wherein the polishing layer would if unfilled have a water uptake of 4 to 8 wt. % after one week of soaking in deionized (DI) water at room temperature. The methods form coplanar metal and dielectric or oxide layer surfaces with low defectivity and a minimized degree of dishing.
1. A CMP polishing pad useful for polishing a metal surface on a semiconductor wafer, the CMP polishing pad comprising:
a porous polishing layer, the porous polishing layer having a top polishing surface, the CMP polishing pad and porous polishing layer consisting essentially of: a cured reaction product of an isocyanate terminated urethane prepolymer, the isocyanate terminated urethane prepolymer being a blend of toluene diisocyanate, polytetramethylene glycol and 4,4′-methylene dicyclohexyl diisocyanate having 8.5 to 9.5 wt. % of unreacted NCO groups; and a curative component consisting essentially of from 60.3 to 70 wt. %, based on the solids weight of the curative component, of a polyol curative having a number average molecular weight of 6,000 to 15,000 and having an average of 5 to 7 hydroxyl groups per molecule; and from 30 to 39.7 wt. %, based on the solids weight of the curative component, of 4,4′ methylene bis (2 chloroaniline), wherein a cured unfilled formulation of the CMP polishing pad lacking porosity, has a water uptake of 4 to 8 wt. % after one week of soaking in deionized (DI) water at room temperature and wherein the polishing layer having the porous top polishing surface has a Shore D hardness ranging of from 28 to 64 according to ASTM D2240 (2015), the top polishing surface being adapted for planarizing and polishing the metal surface of the semiconductor wafer.
2. The CMP polishing pad as claimed in claim 1 , wherein the curative component of the polyol component is 60.6 to 65 wt %, based on the solids weight of the curative component.
3. The CMP polishing pad as claimed in claim 1 , wherein the CMP polishing pad has a Shore D hardness of from 30 to 60.
4. The CMP polishing pad as claimed in claim 1 , wherein the CMP polishing has a Shore D hardness of from 35 to 55.
5. The CMP polishing pad as claimed in claim 1 , wherein the CMP polishing pad comprises CMP polishing stoichiometric ratio of reactive hydrogen groups (defined as sum of NH 2 and OH groups) in the curative component to the unreacted NCO groups in the isocyanate terminated urethane prepolymer ranges from 0.85:1 to 1.15:1.
6. The CMP polishing pad as claimed in claim 1 , wherein the curative is substantially free of any diol.
7. The CMP polishing pad as claimed in claim 1 , wherein the CMP polishing pad has a specific gravity (SG) of from 0.4 to 1.15 and the cured unfilled formulation of the CMP polishing pad has an SG of from 1.1 to 1.2.
8. The CMP polishing pad as claimed in claim 1 , wherein the CMP polishing pad and porous polishing layer comprise gas filled or hollow microelements.