The voltage generated in a noncentrosymmetric crystal due to the bulk photovoltaic effect (BPE) can greatly exceed the energy gap, however, the light energy conversion efficiency is extremely low. Here we show that the BPE is remarkably enhanced in the case of thin films. The measurements of the BPE in heteroepitaxial single domain ferroelectric BaTiO 3 thin films reveal the enhancement of both photoinduced electric field and conversion efficiencies of the BPE by more than 4 orders of magnitude. Besides the fundamental aspect, our results indicate the potential for the use of the BPE in photovoltaic applications.
Because of their immense scalability and manufacturability potential, the HfO2-based ferroelectric films attract significant attention as strong candidates for application in ferroelectric memories and related electronic devices. Here, we report the ferroelectric behavior of ultrathin Hf0.5Zr0.5O2 films, with the thickness of just 2.5 nm, which makes them suitable for use in ferroelectric tunnel junctions, thereby further expanding the area of their practical application. Transmission electron microscopy and electron diffraction analysis of the films grown on highly doped Si substrates confirms formation of the fully crystalline non-centrosymmetric orthorhombic phase responsible for ferroelectricity in Hf0.5Zr0.5O2. Piezoresponse force microscopy and pulsed switching testing performed on the deposited top TiN electrodes provide further evidence of the ferroelectric behavior of the Hf0.5Zr0.5O2 films. The electronic band lineup at the top TiN/Hf0.5Zr0.5O2 interface and band bending at the adjacent n(+)-Si bottom layer attributed to the polarization charges in Hf0.5Zr0.5O2 have been determined using in situ X-ray photoelectron spectroscopy analysis. The obtained results represent a significant step toward the experimental implementation of Si-based ferroelectric tunnel junctions.
Rare earth oxides could represent a valuable alternative to SiO2 in complementary metal–oxide–semiconductor devices. Lu2O3 is proposed because of its predicted thermodynamical stability on silicon and large conduction band offset. We report on the growth by atomic-layer deposition of lutetium oxide films using the dimeric {[C5H4(SiMe3)]2LuCl}2 complex, which has been synthesized for this purpose, and H2O. The films were found to be stoichiometric, with Lu2O3 composition, and amorphous. Annealing in nitrogen at 950°C leads to crystallization in the cubic bixbyite structure. The dielectric constant of the as-grown Lu2O3 layers is 12±1.
Electroresistance in ferroelectric tunnel junctions is controlled by changes in the electrostatic potential profile across the junction upon polarization reversal of the ultrathin ferroelectric barrier layer. Here, hard X-ray photoemission spectroscopy is used to reconstruct the electric potential barrier profile in as-grown Cr/BaTiO3(001)/Pt(001) heterostructures. Transport properties of Cr/BaTiO3/Pt junctions with a sub-μm Cr top electrode are interpreted in terms of tunneling electroresistance with resistance changes of a factor of ∼30 upon polarization reversal. By fitting the I-V characteristics with the model employing an experimentally determined electric potential barrier we derive the step height changes at the BaTiO3/Pt (Cr/BaTiO3) interface +0.42(−0.03) eV following downward to upward polarization reversal.
Since the discovery of ferroelectricity (FE) in HfO2-based thin films, they are gaining increasing attention as a viable alternative to conventional FE in the next generation of non-volatile memory devices. In order to further increase the density of elements in the integrated circuits, it is essential to adopt a three-dimensional design. Since atomic layer deposition (ALD) processes are extremely conformal, ALD is the favored approach in the production of 3D ferroelectric random access memory. Here, we report the fabrication of fully ALD-grown capacitors comprising a 10-nm-thick FE Hf0.5Zr0.5O2 layer sandwiched between TiN electrodes, which are subjected to a detailed investigation of the structural and functional properties. The robust FE properties of Hf0.5Zr0.5O2 films in capacitors are established by several alternative techniques. We demonstrate a good scalability of TiN/Hf0.5Zr0.5O2/TiN FE capacitors down to 100-nm size and the polarization retention in the test “one transistor-one capacitor” (1T-1C) cells after 1010 writing cycles. The presence of a non-centrosymmetric orthorhombic phase responsible for FE properties in the alloyed polycrystalline Hf0.5Zr0.5O2 films is established by transmission electron microscopy. Given the ability of the ALD technique to grow highly conformal films and multilayered structures, the obtained results indicate the route for the design of FE non-volatile memory devices in 3D integrated circuits.
Recently proposed novel neural network hardware designs imply the use of memristors as electronic synapses in 3D cross-bar architecture. Atomic layer deposition (ALD) is the most feasible technique to fabricate such arrays. In this work, we present the results of the detailed investigation of the gradual resistive switching (memristive) effect in nanometer thick fully ALD grown TiN/HfO2/TiN stacks. The modelling of the I-V curves confirms interface limited trap-assisted-tunneling mechanism along the oxygen vacancies in HfO2 in all conduction states. The resistivity of the stack is found to critically depend upon the distance from the interface to the first trap in HfO2. The memristive properties of ALD grown TiN/HfO2/TiN devices are correlated with the demonstrated neuromorphic functionalities, such as long-term potentiation/depression and spike-timing dependent plasticity, thus indicating their potential as electronic synapses in neuromorphic hardware.
The discovery of ferroelectricity in polycrystalline thin films of doped HfO2 has reignited the expectations of developing competitive ferroelectric non-volatile memory devices. To date, it is widely accepted that the...
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