...the jolt of current supplied by the defibrillator unit is DC...
Not quite any more - modern defibrillators use a biphasic shock, basically one cycle of AC.
The principle is the same though - depolarise ALL of the hearts myo-fibrils and conducting system together and hope that organised electrical activity starts up once more.
As to
causing fibrillation the main danger is an electric shock when the heart is trying to repolarise - in fact not just electrical energy can do this. Mechanical shock can do it as well which is why it is
not a myth that a cricket ball landing on one's chest can kill.
In some cases a shock is used to try to convert other rhythms back to normal such as certain fast rhythms which prevent the heart working well (eg ventricular tachycardia) - in this case the shock is synchronised to the "R" wave so as to avoid causing ventricular fibrillation.
Although energies as high as 200J are used in de-fibrillation that's mainly because the body doesn't conduct nearly as well as you'd like in this situation - in open heart surgery paddles are used directly on the heart and only a couple of Joules is needed.
To be honest I'm not sure that it's volts or amps but enough Joules
will kill you.