Urea Derivative-Promoted CsPbl(2)Br Perovskite Solar Cells with High Open-Circuit Voltage

Inorganic perovskite solar cells (PSCs) have witnessed extraordinary advances owing to their prominent stability against thermal aging. However, they suffer from a phase transition from black phase to yellow phase under ambient conditions and serious energy losses relative to the optical bandgap. Herein, urea (Ur) and methyl-substituted urea (Me-Ur) additives are used to modulate the lattice structure and crystallinity of the CsPbI2Br, facilitating phase stability and high device performance. The Me-Ur can attenuate the strong hydrogen bonding networks in the Ur, which leads to stronger coordination of the carbonyl group with undercoordinated Pb2+, more efficiently passivating the defect states and suppressing the lattice distortion of the PbI6 octahedra in the CsPbI2Br perovskite. Consequently, a champion power conversion efficiency of 16.5% with an open-circuit voltage up to 1.33 V is obtained for the CsPbI2Br+Me-Ur-based PSCs, accompanied by enhanced stability under continuous illumination at a temperature of 45 +/- 5 degrees C. These results emphasize the importance of regulating the lattice distortion by the urea derivative to implement efficient and stable inorganic CsPbI2Br PSCs.

Formation and stabilization of all-inorganic perovskites for photovoltaics

Zaiwei Wang

All-inorganic perovskite films hold promise for improving stability of perovskite solar cells. However, the desirable narrow-bandgap inorganic perovskites (such as CsPbI3 and CsPbI2Br) are suffering from the thermodynamic phase instability, as the photoactive black phase (Î±, Î², or Î³ phase) spontaneously transforms into a more thermodynamically stable yellow phase (ÎŽ-phase) in ambient condition, which is limiting the further development of high-performance inorganic PSCs. The stabilization of black phase and the formation of high-quality perovskite films are promoting the remarkable progress for the performance and stability of inorganic perovskite solar cells. Firstly, we show that europium doping of CsPbI2Br stabilizes the black phase of narrow band gap inorganic perovskite at room temperature. We rationalize it by using solid-state nuclear magnetic resonance and high-angle annular dark-field scanning transmission electron microscopy, which show that europium is incorporated into the perovskite lattice. We demonstrate a power-conversion efficiency (PCE) of 13.71% for an inorganic PSC with the composition CsPb0.95Eu0.05I2Br perovskite. Stability tests show that the devices retain 93% of the initial efficiency after 370 hours under maximum power point tracking measurement. Secondly, we demonstrate a function of dopants by adding barium in CsPbI2Br. We find that barium is not incorporated into the perovskite lattice but induces phase segregation, resulting in a change in the iodide/bromide ratio compared to the precursor stoichiometry and consequently a reduction in the band gap energy of the perovskite phase. The device with 20 mol% barium shows a high PCE of 14.0% with a high open-circuit voltage (Voc) of 1.33 V. Then we propose an intermediate-phase engineering strategy to improve the inorganic perovskite/metal oxide interface by utilizing volatile salts. The introduction of organic cations (such as methylammonium and formamidinium), which can be doped into the perovskite lattice, leads to the formation of an organic-inorganic hybrid perovskite intermediate phase, promoting a robust interfacial contact through hydrogen bonding. A champion CsPb(I0.75Br0.25)3-based device with a PCE of 17.0% and a Voc of 1.34 V was realized. Last, the intermediate phase engineering strategy is reported to promote the pure ÃÂ³-phase CsPbI3 perovskite film formation. According to the investigation of the phase transformation processes of pure CsPbI3 and that with different additives, including NH4I, BAI, MAI, FAI and DMAI, we found that the formation of a 3D organic-inorganic hybrid perovskite intermediate phase is essential to avoid the generation of undesired yellow phase and promote the formation of pure black-phase CsPbI3 film. A champion PCE of 17.70% with a stabilized power output of 17.58% based on the optimized CsPbI3-DMAI device is achieved. Overall, we investigate two possible scenarios for element doping: (1) the dopants are incorporated into the crystal lattice for the improvement of stability and efficiency of inorganic PSCs; (2) the dopants form separate phases to induce the halide phase segregation and suppress non-radiative recombination of perovskite films. Besides, based on the formation of 3D organic-inorganic perovskite intermediate phase, we not only promote the formation of pure black phase CsPbI3, but also promotes a robust interfacial contact of inorganic perovskite and metal oxide transport layers.

EPFL2020

Fluorination of Organic Spacer Impacts on the Structural and Optical Response of 2D Perovskites

Pietro Caprioglio, Inés Garcia Benito, Giulia Grancini, Mohammad Khaja Nazeeruddin, Valentin Ianis Emmanuel Queloz

Low-dimensional hybrid perovskites have triggered significant research interest due to their intrinsically tunable optoelectronic properties and technologically relevant material stability. In particular, the role of the organic spacer on the inherent structural and optical features in two-dimensional (2D) perovskites is paramount for material optimization. To obtain a deeper understanding of the relationship between spacers and the corresponding 2D perovskite film properties, we explore the influence of the partial substitution of hydrogen atoms by fluorine in an alkylammonium organic cation, resulting in (Lc)(2)PbI4 and (Lf)(2)PbI4 2D perovskites, respectively. Consequently, optical analysis reveals a clear 0.2 eV blue-shift in the excitonic position at room temperature. This result can be mainly attributed to a band gap opening, with negligible effects on the exciton binding energy. According to Density Functional Theory (DFT) calculations, the band gap increases due to a larger distortion of the structure that decreases the atomic overlap of the wavefunctions and correspondingly bandwidth of the valence and conduction bands. In addition, fluorination impacts the structural rigidity of the 2D perovskite, resulting in a stable structure at room temperature and the absence of phase transitions at a low temperature, in contrast to the widely reported polymorphism in some non-fluorinated materials that exhibit such a phase transition. This indicates that a small perturbation in the material structure can strongly influence the overall structural stability and related phase transition of 2D perovskites, making them more robust to any phase change. This work provides key information on how the fluorine content in organic spacer influence the structural distortion of 2D perovskites and their optical properties which possess remarkable importance for future optoelectronic applications, for instance in the field of light-emitting devices or sensors.

2020

Pulsed laser deposition of (SrBa)Nb2O6 thin films and their properties

Anna Infortuna

Strontium barium niobate (SrxBa1-xNb2O6, shortly SBN) is a solid solution system with tetragonal tungsten bronze crystal structure. It exhibits a ferroelectric phase with only one polar axis and a transition temperature depending on the Sr/Ba ratio. This thesis studies the growth of SBN thin films, in order to obtain a ferroelectric thin film model system for the study of 180° domain switching close to the ferroelectric phase transition. SBN has been chosen not only because uniaxial, but because it is possible to tune the temperature of phase transition varying the Sr/Ba ratio. It is thus possible to study electric properties of the phase transition close to room temperature, where conduction phenomena related to defects are normally lower. Thin films of SBN were grown by Pulsed Laser Deposition in a vacuum system constructed during this thesis work. For the formulation of a model it is desirable to have a system as close as possible to a single crystal. Therefore deposition parameters have been optimized to grow SBN thin films with the polar axis oriented perpendicular to the film plane. The films are integrated in parallel plate capacitor structures, in order to measure dielectric properties. The stability of the ferroelectric phase is found to be sensitive to impurities; contaminants with concentration below 1% induce a lowering of the transition temperature of about 100°C. Strain as well has influence on the phase transition; in the case of substrate with thermal expansion coefficients different from the SBN ones, the SBN film is under stress. A 0.6% tensile strain induces a lowering of the transition temperature of about 100°C, this is the case of silicon single crystal substrate. Grown on strontium titanate single crystals (STO), whose thermo-mechanical properties are close to the one of SBN, the films exhibit a phase transition temperature compatible with the one measured on single crystals. The obtained films suffer from leakage that is reduced by thermal treatment in oxygen rich atmosphere. The oxygen vacancies, created during the deposition process, are considered to be responsible of leakage. Vacancies recovery upon annealing does not eliminate the problem, and measurement of polarization at room temperature is difficult. However, piezoelectric measurements performed on individual grains, with atomic force microscope, prove that these have ferroelectric properties; by these experiment has been proved that it is possible to switch the polarization. Films with a disordered structure of grains are much less leaky than the ones with columnar grains spanning the whole cross section. These observations lead to the conclusion that conduction goes trough the grain boundaries. On STO single crystals, SBN grows epitaxial in Volmer-Weber mode. With a suitable preparation of the substrate surface, it is possible to induce the growth of films with different orientations of the polar axis: in the film plane, perpendicular to it or inclined of 45°. A model is proposed, explaining the epitaxial relation with the substrate on the basis of the perovskite kernel contained in the unit cell of the tetragonal tungsten bronze structure. The film grows from the nucleation of the perovskite structure that rules the orientation of the film; the high temperature at which the substrate is kept during the deposition, assure the necessary mobility for the arriving atoms to organize in the SBN structure around these nuclei. The study of literature data allows to state that such a model is valid not only for substrates with perovskite structure, but can be extended to substrates with a cubic crystal structure, like magnesium oxide.

EPFL2005