n i is the number of atoms from species M (=Ti) being removed from a defect-free cell to its respective

reservoir with chemical potential μ i. The chemical potential reflects the availability or the elemental partial pressure of each element. E F is the reference level according to the valence band level (E v), and ΔV Selleck Alectinib is often simplified as zero. In the present work, the transition metal M substitutes Ti in the calculated models, and the impurity formation energy E form(M) could thus be defined using the following formula [38, 39]: (2) where μ M is the chemical potential of the doping metal. μ Ti is the chemical potential of Ti and depends on the experimental growth condition, which can be Ti-rich or O-rich (or any case in between). Under Ti-rich condition, the Ti chemical potential can be assumed in thermodynamic equilibrium with the energy of bulk Ti, while the O chemical potential can be obtained by the growth condition: (3) Under O-rich condition, the chemical potential of O can be calculated from the ground state energy of O2 molecule, while the chemical potential

of Ti is fixed by Equation (3). The chemical potentials for metals (μ M) are fixed and calculated from the formula below [40, 41]: (4) where is the energy of the most stable oxide for doping atoms at room temperature. The formation energies E form(M) for the 13 different metal-doped models of 24-atom supercell selleck kinase inhibitor under O-rich condition are calculated and listed in Table 2. In terms of the formation enough energy, the transition metals that intend to substitute Ti are in the order of Mo < Zn < Ag < V < Y < Cu < Mn < Nb < Fe < Zr < Cr < Ni < Co under O-rich growth condition. It is difficult to find the tendency of E form(M) with the increase in atomic number in each element period. The formation energies of substitutional Co, Ni, and Cr-doped models are negative and less than those of the models substituted by other transition metals under O-rich growth condition. This indicates that under O-rich growth condition, it is energetically more favorable to replace Ti with Co, Ni, and Cr than other metals.

The synthesis of the Co-, Ni-, and Cr-doped anatase TiO2 system with a higher doping level would be relatively easy in the experiment because a much smaller formation energy is required. This might be because the ionic radii of Cr3+, Co3+, and Ni2+ are close to Ti4+. Presumptively, we suggest that the impurity formation energy is sensitive to the ionic radius of impurity. The results can provide some useful guidance to prepare metal-doped TiO2 and other oxide semiconductors. Table 2 Impurity formation energies of 3 d and 4 d transition metal-doped TiO 2 supercells under O-rich condition Metal doping system μ M/eV E form(M)/eV V/TiO2 -6,141.7221 -1,985.7396 1.5761 Cr/TiO2 -6,247.8894 -2,472.8718 -0.3744 Mn/TiO2 -1,526.5251 -658.4279 1.0589 Fe/TiO2 -3,039.9476 -868.9009 0.4044 Co/TiO2 -1,478.3064 -1,044.2578 -1.3011 Ni/TiO2 -1,789.