Circuit designers use these tools basically daily for two reasons - the first is Layout Versus Schematic. We want to make sure that the physical layout matches the schematic, so the tool turns the layout GDS into a netlist and compares that to the netlist created from the schematic (basically a diff, but more complicated). The second is so we can run simulations that take into account the "parasitic" resistances and capacitances of the wires and metal shapes in the physical layout. It's basically the same procedure as LVS with an extra step that analyzes the metal shapes to determine said R's and C's.
Theoretically Yes, as an ion-beam-mill and electron-microscope combination machine can slice up semiconductors layer-by-layer. Given these machines can often also give precise x-ray analysis material data, the exact makeup of the chip can be extracted by competitors given enough time. =3
Or maybe some kind of hybrid of x-ray microtomography and spectroscopic analysis all in one.
But, maybe the energies involved would be about the same destructive power as some microtome slicing technique...