Band alignment and charge transfer in rutile-TiO2/CH3NH3PbI3-xClx interfaces.

Rutile-TiO2/hybrid halide perovskite CH3NH3PbI3-xClx interfaces are investigated by ab initio density functional theory calculations. The role of chlorine in achieving enhanced solar cell power conversion efficiencies is in the focus of recent studies, which point to increased carrier mobilities, reduced recombination rates, a driven morphology evolution of the perovskite layer and improved carrier transport across the interface. As it was recently established that chlorine is preferentially localized in the vicinity of the interface and not in the bulk of the perovskite layer, we analyze the changes introduced in the electronic properties by varying the chlorine concentration near the interface. In particular, we discuss the effects introduced in the electronic band structure and show the role of chlorine in the enhanced electron injection into the rutile-TiO2 layer. Taking into account these implications, we discuss the conditions for optimizing the solar cell efficiency in terms of interfacial chlorine concentration.

Assessment of structural, optical and conduction properties of ZnO thin films in the presence of acceptor impurities.

The structural, optical and electrical conduction properties of (Li/Cu,N):ZnO codoped thin films synthesized by the sol-gel method were investigated by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD), transmission and absorption, photoluminescence (PL) and I-V measurements in order to bring evidence of the formation of acceptor centers by dual-acceptor codoping processes. The (Li 3%,N 5%):ZnO films consist of crystallites with average size of 15 nm, show 95% transmission in the visible region, and an optical band gap of 3.22 eV. The PL spectra show emission maxima at 3.21 and 2.96 eV which are related to the emission of acceptor centers and the presence of defects, respectively. Li occupies interstitial sites and may form Lii-N(O) defect complexes that act as acceptor centers. The (Cu 3%,N 5%):ZnO films consist of crystallites with average size of 12 nm, and exhibit 90% transmission in the visible region. The PL spectra reveal band edge emission at 3.23 eV and defect related emission at 2.74 eV. In the (Cu,N) codoped films, copper substitutes zinc and adopts mainly the Cu(1+) state. A possible defect complex involving Cu and N determines the transition from n- to p-type conductivity. These findings are in agreement with results of electronic structure calculations at the GGA-PBE level.