tf : The term \'tf\' is not recognized as the name of a cmdlet, function, script file, or operable program. Check the spelling of the name, or if a path
To answer the question form another perspective, this is how you are supposed to call the tf environment variable you created:
tf
%tf%
I've given it the value C:\Windows\notepad.exe, and the application opens when calling the variable from cmd.
C:\Windows\notepad.exe
cmd