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Nb-doped TiO2 (NTO) thin films were sputtered on glass substrate followed by a simple annealing process in air. The photoelectric cooperative optimization was discussed based on the structural, optical and electrical characteristics. The influence of oxygen flow during deposition on materials chemistry and performance was analyzed. Hall measurement showed a strong dependence of transparent conductivity on the oxygen flow. Oxygen vacancies are related to the phase transitions from the rutile to anatase TiO2 during annealing. The chemical states of Nb, Ti and O before and after annealing were discussed. The achievement of optimized transparent conductivity was resultant from the fine-tuning of the doped chemistry and special interplay of dopants and host lattice. [ABSTRACT FROM AUTHOR]