HfO2-based thin films hold huge promise for integrated devices as they show full compatibility with semiconductor technologies and robust ferroelectric properties at nanometer scale. While their polarization switching behavior has been widely investigated, their electromechanical response received much less attention so far. Here, we demonstrate that piezoelectricity in Hf0.5Zr0.5O2 ferroelectric capacitors is not an invariable property but, in fact, can be intrinsically changed by electrical field cycling. Hf0.5Zr0.5O2 capacitors subjected to ac cycling undergo a continuous transition from a positive effective piezoelectric coefficient d33 in the pristine state to a fully inverted negative d33 state, while, in parallel, the polarization monotonically increases. Not only can the sign of d33 be uniformly inverted in the whole capacitor volume, but also, with proper ac training, the net effective piezoresponse can be nullified while the polarization is kept fully switchable. Moreover, the local piezoresponse force microscopy signal also gradually goes through the zero value upon ac cycling. Density functional theory calculations suggest that the observed behavior is a result of a structural transformation from a weakly-developed polar orthorhombic phase towards a well-developed polar orthorhombic phase. The calculations also suggest the possible occurrence of a non-piezoelectric ferroelectric Hf0.5Zr0.5O2. Our experimental findings create an unprecedented potential for tuning the electromechanical functionality of ferroelectric HfO2-based devices.
The wake-up behavior and ON/OFF current ratio of TiN-Al2O3-Hf0.5Zr0.5O2-W ferroelectric tunnel junction (FTJ) devices were investigated for different wake-up voltage waveforms. We studied triangular and square waves, as well as square pulse trains of equal or unequal voltage amplitudes for positive and negative polarities. We find that the wake-up behavior in these FTJ stacks is highly influenced by the field cycling waveform. A square waveform is observed to provide wake-up with the lowest number of cycles, concomitantly resulting in higher remnant polarization and a higher ON/OFF ratio in the devices, compared to a triangular waveform. We further show that wake-up is dependent on the number of cycles rather than the total time of the applied electric field during cycling. We also demonstrate that different voltage magnitudes are necessary for positive and negative polarities during field cycling for efficient wake-up. Utilizing an optimized waveform with unequal magnitudes for the two polarities during field cycling, we achieve a reduction in wake-up cycles and a large enhancement of the ON/OFF ratio from â¼5 to â¼35 in our ferroelectric tunnel junctions.
Conductive bridge random access memory devices such as Cu/SiO2/W are promising candidates for applications in neuromorphic computing due to their fast, low-voltage switching, multiple-conductance states, scalability, low off-current, and full compatibility with advanced Si CMOS technologies. The conductance states, which can be quantized, originate from the formation of a Cu filament in the SiO2electrolyte due to cation-migration-based electrochemical processes. A major challenge related to the filamentary nature is the strong variability of the voltage required to switch the device to its conducting state. Here, based on a statistical analysis of more than hundred fifty Cu/SiO2/W devices, we point to the key role of the activation energy distribution for copper ion diffusion in the amorphous SiO2. The cycle-to-cycle variability is modeled well when considering the theoretical energy landscape for Cu diffusion paths to grow the filament. Perspectives of this work point to developing strategies to narrow the distribution of activation energies in amorphous SiO2.
Inversely tapered silicon photonic resonators on silicon substrates were shown to host multiple high-Q whispering gallery modes and constitute versatile building blocks for CMOS compatible solid state lighting, optical sensing and modulator devices. So far, numerical analyses by the finite difference time domain method have been used to predict the height distribution of whispering gallery modes in such resonators. In this study, we provide an experimental evidence of this mode distribution along the resonator height by selectively exciting whispering gallery modes using cathodoluminescence spectroscopy. Further we derive analytical functions that permit to relate the height distribution of modes with a defined polarization, symmetry and effective refractive index to the geometrical shape of the inversely tapered resonators.
Memristive devices, whose conductance depends on previous programming history, are of significant interest for building nonvolatile memory and brain-inspired computing systems. Here, we report half-integer quantized conductance transitions G = (n/2) (2e(2)/h) for n = 1, 2, 3, etc., in Cu/SiO2/W memristive devices observed below 300 mV at room temperature. This is attributed to the nanoscale filamentary nature of Cu conductance pathways formed inside SiO2. Retention measurements also show spontaneous filament decay with quantized conductance levels. Numerical simulations shed light into the dynamics underlying the data retention loss mechanisms and provide new insights into the nanoscale physics of memristive devices and trade-offs involved in engineering them for computational applications.
SrTiO3 epitaxial growth by molecular beam epitaxy (MBE) on silicon has opened up the route to the monolithic integration of various complex oxides on the complementary metal-oxide-semiconductor silicon platform. Among functional oxides, ferroelectric perovskite oxides offer promising perspectives to improve or add functionalities on-chip. We review the growth by MBE of the ferroelectric compound BaTiO3 on silicon (Si), germanium (Ge) and gallium arsenide (GaAs) and we discuss the film properties in terms of crystalline structure, microstructure and ferroelectricity. Finally, we review the last developments in two areas of interest for the applications of BaTiO3 films on silicon, namely integrated photonics, which benefits from the large Pockels effect of BaTiO3, and low power logic devices, which may benefit from the negative capacitance of the ferroelectric.
Epitaxial growth of SrTiO3 on silicon by molecular beam epitaxy has opened up the route to the integration of functional complex oxides on a silicon platform. Chief among them is ferroelectric functionality using perovskite oxides such as BaTiO3. However, it has remained a challenge to achieve ferroelectricity in epitaxial BaTiO3 films with a polarization pointing perpendicular to the silicon substrate without a conducting bottom electrode. Here, we demonstrate ferroelectricity in such stacks. Synchrotron X-ray diffraction and high-resolution scanning transmission electron microscopy reveal the presence of crystalline domains with the long axis of the tetragonal structure oriented perpendicular to the substrate. Using piezoforce microscopy, polar domains can be written and read and are reversibly switched with a phase change of 180°. Open, saturated hysteresis loops are recorded. Thus, ferroelectric switching of 8- to 40-nm-thick BaTiO3 films in metal-ferroelectric-semiconductor structures is realized, and field-effect devices using this epitaxial oxide stack can be envisaged.
Epitaxial rare earth manganite thin films (ReMnO(3); Re = Tb, Ho, Er, and Y) and multilayers were grown by liquid injection metal organic chemical vapor deposition (MOCVD) on YSZ(111) and the same systems were grown c-oriented on Pt(111) buffered Si substrates. They have been structurally investigated by electron diffraction (ED) and high resolution transmission electron microscopy (HRTEM). Nanodomains of secondary orientation are observed in the hexagonal YMnO(3) films. They are related to a YSZ(111) and Pt(111) misorientation. The epitaxial film thickness has an influence on the defect formation. TbO(2) and Er(2)O(3) inclusions are observed in the TbMnO(3) and ErMnO(3) films respectively. The structure and orientation of these inclusions are correlated to the resembling symmetry and structure of film and substrate. The type of defect formed in the YMnO(3)/HoMnO(3) and YMnO(3)/ErMnO(3) multilayers is also influenced by the type of substrate they are grown on. In our work, atomic growth models for the interface between the film/substrate are proposed and verified by comparison with observed and computer simulated images.
