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Not necessarily. There are lots of comparisons to submarines but it's more comparable to airplanes. Part of the security on a plane is that it is physically impossible to open the door while the plane is flying. The pressure difference between the pressurized inside and thin air outside would require superhuman force to open.
In a similar vein, when the ISS was constructed it wasn't initially pressurized. This would make opening the door from the outside trivial from a pressurization standpoint. As long as the only means to pressurize it could be triggered from inside, there'd be no way it would be pressurized without someone inside.
Is it physically impossible or physically impossible for a human? Obviously something can punch a hole through it, but is the material not strong enough to sustain the force needed for it and to hold together?
Physically impossible to open the door in a fashion it was meant to be. Airplane doors are designed to open inwards. The air pressure inside the plane pushed the door into place evenly over the entire surface. Given an approximate pressure differential of 8psi spread across a minimum 24x48" airplane for would be 10,752 pounds of force that would need to be overcome to open the door. There is no way to apply that kind of force from inside the plane that wouldn't catastrophically damage the door prior to opening. You can't just pull the handle that hard without it breaking. There'd be nothing to grab that would pull out in without failure.
So maybe you could rig up a machine to break a portion of the door and create a hole. But the door would in no way be intact or functional afterwards.
For a human. By having doors open towards the side with the higher pressure it makes actually moving the door exceptionally difficult even if the handle is actuated to allow it to open. I'm also pretty sure that most airplanes have mechanical latches that prevent the handle from moving to the open position as well.
However, everything is possible with enough and properly applied forces. You may not end up with the door in the same shape you started with though.
That is a super cool implementation of physics.