Similar problem( i have complex configurations of anode in Schottky Diode: there are two types conducter - aluminum and molibdenum. So athena undefine such type material (Mb). But when i create it like a new own material, nothing does work. Manual says: All user-defined materials from ATHENA, irrespective of the material name chosen by the user, will also become such insulator materials.
Unfortunatly i couldn't find how to change it( The list of standart conducters and other materials depend on version your software package. So i just choose standart material, whitch have simular proportes in case my modeling aim - that was Tungsten. After that i change material charecteristics (work function) when make dc-analysis. Hope it's help you. Sorry for my bad english