Despite symmetrical polarization, the magnitude of a light-induced voltage is known to be asymmetric with respect to poling sign in many photovoltaic (PV) ferroelectrics (FEs). This asymmetry remains unclear and is often attributed to extrinsic effects. We show here for the first time that such an asymmetry can be intrinsic, steaming from the superposition of asymmetries of internal FE bias and electro-piezo-strictive deformation. This hypothesis is confirmed by the observed decrease of PV asymmetry for smaller FE bias. Moreover, the both PV effect and remanent polarization are found to increase under vacuum-induced expansion and to decrease for gas-induced compression, with tens percents tunability. The change in cations positions under pressure is analysed through the first-principle density functional theory calculations. The reported properties provide key insight for FE-based solar elements optimization.

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Hybrid organometallic systems offer a wide range of functionalities, including magnetoelectric (ME) interactions. However, the ability to design on-demand ME coupling remains challenging despite a variety of host-guest configurations and ME phases coexistence possibilities. Here, we report the effect of metal-ion substitution on the magnetic and electric properties in the paramagnetic ferroelectric NH2(CH3)2Al1−xCrx(SO4)2 × 6H2O. Doing so we are able to induce and even tune a sign of the ME interactions, in the paramagnetic ferroelectric (FE) state. Both studied samples with x = 0.065 and x = 0.2 become paramagnetic, contrary to the initial diamagnetic compound. Due to the isomorphous substitution with Cr the ferroelectric phase transition temperature (T c) increases nonlinearly, with the shift being larger for the 6.5% of Cr. A magnetic field applied along the polar c axis increases ferroelectricity for the x = 0.065 sample and shifts T c to higher values, while inverse effects are observed for x = 0.2. The ME coupling coefficient αME = 1.7 ns/m found for a crystal with Cr content of x = 0.2 is among the highest reported up to now. The observed sign change of αME with a small change in Cr content paves the way for ME coupling engineering.

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The recently reported ability to induce and tune a sign of the magnetoelectric (ME) interactions in NH2(CH3)2Al1−xCrx(SO4)2 · 6H2O crystals as a function of Cr content is further investigated here. The ME coupling and its larger absolute value for the sample with larger Cr content agrees qualitatively with thermodynamic Landau analysis. However, quantitative estimation implies other contributions as well. The observed nontrivial magnetic field dependence of ferroelectric transition can be explained within the model that takes into account influence of the arising local deformation of the lattice on the two types of DMA group responsible respectively for the ferroelectric and antiferroelectric ordering.