$PATH environment variable does not seem to be recognized

I've made a fresh install of Debian Wheezy, and installed zsh to it. Few days after, I've done a vanilla installation of TeX Live 2014, so I added the necessary binary paths to my $PATH. Now I started writing little scripts so I would like to put them somewhere easily accessible, that is ~/bin. My path looks like this: ~/bin:/opt/texbin:/usr/local/bin:/usr/bin:/bin:/usr/local/games:/usr/games Now, if I wanted to run something from TeX Live, it's easy: % which pdflatex /opt/texbin/pdflatex No problem. But when I try running something from ~/bin, ... % which hello_world hello_world not found So I double-checked: % ls -l ~/bin total 18 -rwxr-xr-x 1 bozbalci bozbalci 5382 Sep 8 00:28 hello_world And it shows that hello_world is doing fine in ~/bin with its execution permissions set. I've tried rehash, but it didn't work. Help?