The paper considers new effects of the nanoscale state of matter, which open up prospects for the creation of electronic devices using new physical principles. The contact of chemically homogeneous different sizes hydrated nanoparticles of yttrium-stabilized zirconium oxide (ZrO2 – x %mol Y2O3, x=0, 3, 4, 8; YSZ) with particle sizes of 7.5 nm and 7,5 nm; 7.5 nm and 9 nm; 7.5 nm and 11 nm; 7.5 nm and 14 nm in the form of compacts obtained using high hydrostatic pressure (HP-compacts of 300MPa) was studied at direct and alternating current. A unique size effect of the nonlinear (semiconductor) dependence of the electrical properties (in the region U <2.5 V, I ≤ 2.7 mA) of the contact of different-sized YSZ nanoparticles of the same chemical composition is revealed, which indicates the possibility of creating semiconductor structures of a new type based on chemically homogeneous nanostructured systems. The electronic structure of the near-surface regions of nanoparticles of a special type of oxide materials and the possibility, on this basis, to obtain specifically rectifying properties of the contacts were studied theoretically. Models of surface states of the Tamm type are constructed, but considering the Coulomb long-range action. The discovered variance and its dependence on the curvature of the surface of nanoparticles made it possible to study the conditions for the formation of a contact potential difference in cases of nanoparticles of the same radius (synergistic effect), different radii (doped and undoped variants), as well as to discover the possibility of describing a group of powder particles from material within the Anderson model. The established effect makes it possible to solve the problem of diffusion instability of semiconductor heterojunctions and opens up prospects for creating electronics devices with a fundamentally new level of properties for use in various fields of the national economy and breakthrough critical technologies.