Here's a few:

Brainstorm - shows the progression of developing technology (in this case a device that can record and playback a subjects' experiences.)

Real Genius - College antics with a bunch of kids developing a stronger laser

Silicon Valley - mini series again about silicon valley culture/developing new tech - also how ideas are discovered and others stumble upon similar, etc.

American Experience: Silicon Valley - documentary of early silicon valley and the people who started the companies