Wheat flour consists of two major proteins—glutenin and gliadin
When you add water to the flour and knead it, it leads to the formation of an a continuous network of the protein Gluten, which lends the dough elasticity and makes it stretchable.
The strong gluten network is also capable of trapping gas bubbles within the bread (roti in our case)
When we flatten and cook the roti on the girdle, the steam produced inside the roti causes it to puff up as the pressure from the steam pushes the gluten network outward.
In short, well-kneaded dough (so that a long protein network is formed), reasonable moisture and a reasonably high cooking temperature combine to make your rotis puff. If the dough isn't well kneaded or if the rotis are cooked on low heat, they'll most likely not puff well.