Materials containing picocrystalline quantum dots that form artificial atoms are disclosed. The picocrystalline quantum dots (in the form of boron icosahedra with a nearly- symmetrical nuclear configuration) can replace corner silicon atoms in a structure that demonstrates both short range and long-range order as determined by x-ray diffraction of actual samples. A novel class of boron-rich compositions that self-assemble from boron, silicon, hydrogen and, optionally, oxygen is also disclosed. The preferred stoichiometric range for the compositions is (B12Hw)x Siy Oz with 3 ≤ w ≤ 5, 2 ≤ x ≤ 4, 2 ≤ y ≤ 5 and 0 ≤ z ≤ 3. By varying oxygen content and the presence or absence of a significant impurity such as gold, unique electrical devices can be constructed that improve upon and are compatible with current semiconductor technology.