The correct option is D Sample X is undoped while samples Y and Z have been doped with a fifth group and a third group impurity respectively.
There is no extra energy level in between conduction and valence bands, in sample X. Clearly, it is an intrinsic silicon, i.e. undoped silocon.
In sample Y, the extra energy level lies near the bottom of the conduction band, so it is a N−type semiconductor and has been doped with an element from the fifth group.
In sample Z, the extra energy level lies near the top of the valence band, so it is a P−type semiconductor and has been doped with an element from the third group.
Hence, (D) is the correct answer.