Modifying work function of a metal film with a plasma process

Abstract

A sequential plasma process is employed to enable the modification of the work function of a p-type metal layer in a metal gate structure. The sequential plasma process includes a plasma hydrogenation and a plasma process that includes electronegative species. The sequential plasma process is performed on a p-type metal layer in a film stack, thereby replacing suboxides and/or other non-stoichiometrically combined electronegative atoms disposed on or within layers of the film stack with stoichiometrically combined electronegative atoms, such as O atoms. As a result, the work function of the p-type metal layer can be modified without changing a thickness of the p-type metal layer.

1 . A method of forming a transistor, the method comprising:
 depositing a high-k dielectric layer over a surface of a semiconductor material, wherein the surface of the semiconductor material has a first work function value;   after depositing the high-k dielectric layer, depositing a p-type metal layer over the semiconductor material and the high-k dielectric layer, wherein the p-type metal layer has an exposed surface and a second work function value;   exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species to change the first work function value to a third work function value,   wherein the third work function value is between the first work function value and the second work.   
     
     
         2 . The method of  claim 1 , wherein the p-type metal layer comprises a metal capping layer that is deposited on the high-k dielectric layer. 
     
     
         3 . The method of  claim 2 , further comprising, after exposing the exposed surface of the p-type metal layer to plasma-excited species, depositing a different p-type metal layer on the exposed surface. 
     
     
         4 . The method of  claim 3 , wherein the different p-type metal layer comprises a work function layer that is deposited on the metal capping layer. 
     
     
         5 . The method of  claim 3 , further comprising, after exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species and prior to depositing the different p-type metal layer on the exposed surface, exposing the exposed surface to air. 
     
     
         6 . The method of  claim 1 , wherein exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species comprises stoichiometrically adding atoms from the electronegative species to the p-type metal layer. 
     
     
         7 . The method of  claim 1 , wherein depositing the p-type metal layer comprises:
 depositing a first p-type metal layer on the high-k dielectric layer; and   depositing a second p-type metal layer on the first p-type metal layer,   wherein exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species comprises exposing an exposed surface of the second p-type metal layer to the plasma-excited electronegative species.   
     
     
         8 . The method of  claim 1 , wherein the plasma-excited electronegative species include atoms having a Paulding electronegativity of at least about 2.5 
     
     
         9 . The method of  claim 1 , wherein the plasma-excited electronegative species include at least one of an oxygen-containing species, a nitrogen-containing species, and a fluorine-containing species. 
     
     
         10 . The method of  claim 1 , wherein the p-type metal layer comprises a metal with a work function value that is equal to or greater than the first work function value. 
     
     
         11 . The method of  claim 1 , further comprising, prior to exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species, exposing the exposed surface to plasma-excited hydrogen species to remove electronegative atoms from the p-type metal layer. 
     
     
         12 . The method of  claim 11 , wherein exposing the exposed surface to plasma-excited hydrogen species comprises forming vacancies in the p-type metal layer. 
     
     
         13 . The method of  claim 12 , wherein exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species comprises filling the formed vacancies in the p-type metal layer with electronegative atoms. 
     
     
         14 . The method of  claim 11 , wherein the exposed surface is not exposed to air after being exposed to the plasma-excited hydrogen species and before being exposed to the plasma-excited electronegative species. 
     
     
         15 . The method of  claim 11 , wherein the exposed surface is exposed to the plasma-excited hydrogen species and to the plasma-excited electronegative species in a same processing chamber. 
     
     
         16 . The method of  claim 1 , wherein the plasma-excited electronegative species are formed by use of an inductively coupled plasma that is disposed adjacent to a surface of the exposed surface of the p-type metal layer. 
     
     
         17 . The method of  claim 1 , further comprising, prior to exposing the exposed surface of the p-type metal layer to plasma-excited electronegative species, performing a plasma-based conditioning process on a process chamber in which the exposed surface is exposed to the plasma-excited electronegative species. 
     
     
         18 . The method of  claim 17 , wherein the plasma-based conditioning process is performed on the process chamber when a semiconductor substrate on which the p-type metal layer is deposited is not disposed within the process chamber.