Ive been doing some research while it is rainy out, regarding generating electricity with heat from the sun..
There are lots of ways to generate electricity from heat, but for the most part they dont seem cost-effective for the do-it-yourselfer to piece together.
As far as the actual semiconductor you want to use, from what I have found Bismuth (III) Telluride is the best available. Here is an excerpt from the Wikipedia page (with references for you skeptics)
The properties relevant to thermoel....

Do It Yourself Solar