RESUMO
Memories based on the insulator-to-metal transition in correlated insulators are promising to overcome the limitations of alternative nonvolatile memory technologies. However, associated performances have been demonstrated so far only on narrow-gap compounds, such as (V0.95Cr0.05)2O3, exhibiting a tight memory window. In the present study, V-substituted Cr2O3 compounds (Cr1-xVx)2O3 have been synthesized and widely investigated in thin films, single crystals, and polycrystalline powders, for the whole range of chemical composition (0 < x < 1). Physicochemical, structural, and optical properties of the annealed magnetron-sputtered thin films are in very good agreement with those of polycrystalline powders. Indeed, all compounds exhibit the same crystalline structure with a cell parameter evolution consistent with a solid solution over the whole range of x values, as demonstrated by X-ray diffraction and Raman scattering. Moreover, the optical band gap of V-substituted Cr2O3 compounds decreases from 3 eV for Cr2O3 to 0 eV for V2O3. In the same way, resistivity is decreased by almost 5 orders of magnitude as the V content x is varying from 0 to 1, similarly in thin films and single crystals. Finally, a reversible resistive switching has been observed for thin films of three selected V contents (x = 0.30, 0.70, and 0.95). Resistive switching performed on MIM devices based on a 50 nm thick (Cr0.30V0.70)2O3 thin film shows a high endurance of 1000 resistive switching cycles and a memory window ROFF/RON higher by 3 orders of magnitude, as compared to (Cr0.05V0.95)2O3. This comprehensive study demonstrates that a large range of memory windows can be reached by tuning the band gap while varying the V content in the (Cr1-xVx)2O3 solid solution. It thus confirms the potential of correlated insulators for memory applications.
RESUMO
Ambipolar materials such as carbon nanotubes, graphene, or 2D transition metal chalcogenides are very attractive for a large range of applications, namely, light-emitting transistors, logic circuits, gas sensors, flash memories, and solar cells. In this work, it is shown that the nanoarchitectonics of inorganic Mo6 cluster-based iodides enable to form thin films exhibiting photophysical properties that enable their classification as new members of the restricted family of ambipolar materials. Thus, the electronic properties of the ternary iodide Cs2[{Mo6I8i}I6a] and those of thin films of the aqua-complex-based compound [{Mo6I8i}I4a(H2O)2a]·xH2O were investigated through an in-depth photoelectrochemical study. Once hole/electron pairs are created, the holes and electrons turn to be transported simultaneously in opposite directions, and their lifetimes exhibit similar values. The ambipolar properties were demonstrated via the integration of [{Mo6I8i}I4a(H2O)2a]·xH2O as light harvesters in an all-solid solar cell. A significant photoresponse with a typical diode characteristic clearly provides evidence of the simultaneous transfer and transport of holes and electrons within the [{Mo6I8i}I4a(H2O)2a]·xH2O layer. The ambipolar behavior results, on the one hand, from the confinement of electrons imposed by the nanometric size of the molecular metal clusters and, on the other hand, from the poor electronic interactions between clusters in the solid state. Such molecular structure-based layers lead naturally to an intrinsic semiconducting behavior.