Ab initio modeling of copper adhesion on regular BaTiO3(001) surfaces

A comparative ab initio study of Cu overlayers on BaTiO3(001) and MgO(001) substrates

“…Our estimate of the adsorption energy for Cu/BaTiO 3 interface (0.9-1.1 eV in Table 1) is in qualitative agreement with this trend when we consider the values calculated for Pd/SrTiO 3 (001) (2.5 eV [18]) and Pt/BaTiO 3 (001) (3.9 eV [16]) interfaces. Despite the fact that the adsorption energy in Cu/MgO(001) interface is noticeably smaller as compared to that for both the terminations of Cu/BaTiO 3 interface (Table 1), the interfacial distances are qualitatively similar to those calculated earlier for various metals upon strontium and barium titanate (1.9-2.1 Å [16][17][18][19]). We found that for the same coverage densities, Cu adatoms are bound somewhat more strongly upon the TiO 2 -terminated surfaces than on the BaO termination, mainly due to a strong influence of surface Ti ions.…”

“…Calculations on both periodic (slab) [10, 14 -20] and cluster (embedded and molecular [9 -13]) models were performed using either Hartree -Fock (HF) [10,17] or Density Functional Theory (DFT) [9, 11-16, 18, 19] methods. In these calculations the ordered metal adlayers of different atomic densities and single Cu or few adatoms were simulated, respectively.…”

“…Moreover, the structure modifications in a perovskite contact with a metal [6] could be also much larger than ferroelectric-cubic differences. This is why in the theoretical modeling of the BaTiO 3 interfaces with metals (Ta, W, Ir, Pt [16] and Cu [17]) small ferroelectric distortions of the perovskite surface structure were neglected. A simple cubic structure was considered here for a low (≤0.5 ML) coating by an adsorbed metal (note that for BaOterminated surface, 0.5 net ML pattern of fcc metal atoms cover all surface oxygen ions, as shown in Fig.…”

“…In our previous studies of these systems we have employed a one-side metal adsorption model in slab calculations using two different computational LCAO (linear combination of atomic orbitals) formalisms as implemented in CRYSTAL-2003 code [27]: (i) the hybrid B3LYP DFT method for Cu/MgO(001) [15] and (ii) the HF method with a posteriori electron correlation corrections (HF-CC) for Cu on both BaO-and TiO 2 -terminated BaTiO 3 [17]. For a reliable comparison of Cu adhesion on these two oxide surfaces, we have used here the same two-sided adsorption slab models with identical metal submonolayer coverages and the same DFT-LCAO method (with hybrid B3PW Hamiltonian).…”

Periodic models in quantum chemical simulations of F centers in crystalline metal oxides

“…Prior to the deposition, the substrates are usually prepared in such a way that predominantly TiO 2 ‐terminated (001) surfaces are expected to occur 187. So far, only two series of ab initio calculations on periodic models of interfaces between pure cubic BaTiO 3 (001) substrate and deposited metals were presented in the literature 180, 188. In the former study, DFT‐PW calculations were performed on the interface between Ta, W, Ir, or Pt metals and the BaO‐terminated surface.…”