As a materialist, you need a scientist with Psionic Expertise trait, assigned to social research. Only to
unlock the chance to roll Psi Theory tech, but chances are still very slim, until you researched almost any another non-repeatable tech in Social tree. The chance is somewhat bigger only than the chance of rolling up the repeatable tech after completing another repeatable.
http://www.stellariswiki.com/Technology
All Psi techs following Psi Theory aren't so restricted to roll their card, so, all your efforts are literally just to get Psi Theory.
That's the terrible drawback of Stellaris's materialism - while not-a-materialist literally getting Psi Theory just after others non-repeatable techs (due to chance numbers), materialist should get the trait by any means.
How to get the trait?
Scientists can't have the trait from the start, i.e. on the hire screen. They have to develop this feature on their own.
Two ways:
1. randomly get on scientist's level-up;
2. get luck with very specific and rare random encounter during surveying of star systems.
Let's stop at levelling up your scientists.
You could send science ships into the unknown to survey the world. This also includes the chance to get specific encounter. But we have a faster way.
Assist research.
1. Hire scientists with whatever trait they have from the start, you limited only with your influence and Leader Capacity number;
2. build a science ship for every scientist;
3. assign scientist to ships and send them assist research - don't matter where to, even to colony without any science productivity, scientists will get exp on the time basis;
4. as they getting levelups, you'll get notifications about that and pop-up window if scientist got a trait. If the scientist get 5th level, didn't get Psi Expertise and you have influence to hire another one - dismiss&hire.
Is it worth to unassign scientists from researching in order to increase the "level-up pool"?
I don't know. Can't recommend it tho.