I have had to build out a material file in Silvaco before. The user manual gives a reasonably good breakdown on how this is achieved. The following is some example code for a new material called "high_dielectric":
go atlas
mesh ...
region num=1 x.min=1 x.max=2 y.min=0 y.max=2 user.material=high_dielectric
electrode ...
doping ...
material material=high_dielectric user.group=insulator user.default=oxide permittivity=ENTER YOUR VALUES HERE
Basically you define its name (user.material) and define it as a semiconductor, insulator or conductor (user.group). Additionally, you can find a material which is defined by Atlas and base your material off of it (this helps if you don't know all of the material parameters) by using "user.default=some_material". You can then define any specific material parameters using the "material" statement.
What are you trying to simulate? If, for example, you are trying to simulate a FET with a user defined high dielectric material, then I would suggest starting from one of the many examples silvaco has available and then modifying it using the method I detailed in my previous answer. The advantage of doing it this way is that you will know the electrodes etc. are setup properly.
I am simulating a TFET and I want to replace the cavity region with different dielectric constants so I want to know how to define that region with different values of dielectric constant and vary the values