You've really already got the only two "safe", "effective" options available: helium and argon. And I put both words in quotes for a reason.
Although the much lesser density of helium raises the pitch of your voice, I've never heard someone on argon with a deeper voice. I always assumed it would work, but no one has ever confirmed it for me.
As to safety, the gas people use to inflate party balloons isn't pure helium. There's plenty of air, and just enough helium to add buoyancy. Pure helium is too expensive to use for party balloons. So that's why its safe to breathe. I don't know who mixes air with argon into a safe and effective voice modulator, or if argon's density make it dangerous to breathe in any mix.