There are a number of different ways to show that a local diffeomorphism $f: X \rightarrow Y$ is a global diffeomorphism: For example, this follows if $X$ and $f(X)$ are both connected and simply connected. Or if $X$ and $Y$ are both simply connected compact manifolds without boundary. I think but am not sure that the statement also follows if $X$ and $Y$ are both simply connected manifolds without boundary and the map $f$ is proper.