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Intrinsic ferroelectricity in Y-doped HfO2 thin films

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 Added by Xiaoshan Xu
 Publication date 2021
  fields Physics
and research's language is English




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Ferroelectric HfO2-based materials hold great potential for widespread integration of ferroelectricity into modern electronics due to their robust ferroelectric properties at the nanoscale and compatibility with the existing Si technology. Earlier work indicated that the nanometer crystal grain size was crucial for stabilization of the ferroelectric phase of hafnia. This constraint caused high density of unavoidable structural defects of the HfO2-based ferroelectrics, obscuring the intrinsic ferroelectricity inherited from the crystal space group of bulk HfO2. Here, we demonstrate the intrinsic ferroelectricity in Y-doped HfO2 films of high crystallinity. Contrary to the common expectation, we show that in the 5% Y-doped HfO2 epitaxial thin films, high crystallinity enhances the spontaneous polarization up to a record-high 50 {mu}C/cm2 value at room temperature. The high spontaneous polarization persists at reduced temperature, with polarization values consistent with our theoretical predictions, indicating the dominant contribution from the intrinsic ferroelectricity. The crystal structure of these films reveals the Pca21 orthorhombic phase with a small rhombohedral distortion, underlining the role of the anisotropic stress and strain. These results open a pathway to controlling the intrinsic ferroelectricity in the HfO2-based materials and optimizing their performance in applications.

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HfO2, a simple binary oxide, holds ultra-scalable ferroelectricity integrable into silicon technology. Polar orthorhombic (Pbc21) form in ultra-thin-films ascribes as the plausible root-cause of the astonishing ferroelectricity, which has thought not attainable in bulk crystals. Though, perplexities remain primarily due to the polymorphic nature and the characterization challenges at small-length scales. Herein, utilizing a state-of-the-art Laser-Diode-heated Floating Zone technique, we report ferroelectricity in bulk single-crystalline HfO2:Y as well as the presence of anti-polar Pbca phase at different Y concentrations. Neutron diffraction and atomic imaging demonstrate (anti-)polar crystallographic signatures and abundant 90o/180o ferroelectric domains in addition to the switchable polarization with little wake-up effects. Density-functional theory calculations suggest that the Yttrium doping and rapid cooling are the key factors for the desired phase. Our observations provide new insights into the polymorphic nature and phase controlling of HfO2, remove the upper size limit for ferroelectricity, and also pave a new road toward the next-generation ferroelectric devices.
We studied the ferroelectric and ferromagnetic properties of compressive strained and unstrained BiMnO3 thin films grown by rf-magnetron sputtering. BiMnO3 samples exhibit a 2D cube-on-cube growth mode and a pseudo-cubic struc-ture up to a thickness of 15 nm and of 25 nm when deposited on (001) SrTiO3 and (110) DyScO3, respectively. Above these thicknesses we observe a switching to a 3D island growth and a simultaneous structural change to a monoclinic structure characterized by a (00l) orientation of the monoclinic unit cell. While ferromagnetism is observed below Tc = 100 K for all samples, signatures of room temperature ferroelectricity were found only in the pseudo-cubic ultra-thin films, indicating a correlation between electronic and structural orders.
Ferroelectricity at room temperature has been demonstrated in nanometer-thin quasi 2D croconic acid thin films, by the polarization hysteresis loop measurements in macroscopic capacitor geometry, along with observation and manipulation of the nanoscale domain structure by piezoresponse force microscopy. The fabrication of continuous thin films of the hydrogen-bonded croconic acid was achieved by the suppression of the thermal decomposition using low evaporation temperatures in high vacuum, combined with growth conditions far from thermal equilibrium. For nominal coverages >=20 nm, quasi 2D and polycrystalline films, with an average grain size of 50-100 nm and 3.5 nm roughness, can be obtained. Spontaneous ferroelectric domain structures of the thin films have been observed and appear to correlate with the grain patterns. The application of this solvent-free growth protocol may be a key to the development of flexible organic ferroelectric thin films for electronic applications.
Ferroelectric HfO2 (fe-HfO2) has garnered increasing research interest for nonvolatile memories and low-power transistors. However, many challenges are to be resolved. One of them is the depolarizing effect that is commonly attributed to the formation of fe-HfO2: electrode interface. In addition to this interface, it is not hard to find that HfO2 is rarely used in isolation but most often in combination with non-ferroelectric dielectric in real device for practical reasons. This leads to the formation of fe-HfO2: dielectric interface. Recently, counterintuitive enhancement of ferroelectricity in fe-HfO2 grown on SiO2 has been discovered experimentally, opening up a previously unknown region in design space. Yet, a deeper understanding of the role of SiO2 in enabling the enhanced ferroelectricity in fe-HfO2 still lacks. Here, we investigate the electronic structures of ten fe-HfO2: oxide dielectric interfaces. We find that while in most cases, as expected, interface formation introduces depolarizing fields in fe-HfO2, SiO2 and GeO2 stand out as two abnormal dielectrics in the sense that they surprisingly hyperpolarize fe-HfO2, in consistence with the experimental findings. We provide explanations from a chemical bonding perspective. This work suggests that the interplay between fe-HfO2 and non-ferroelectric dielectric is nontrivial and cannot be neglected toward an improved understanding of HfO2 ferroelectricity.
BaSnO_{3}, a high mobility perovskite oxide, is an attractive material for oxide-based electronic devices. However, in addition to low-field mobility, high-field transport properties such as the saturation velocity of carriers play a major role in determining device performance. We report on the experimental measurement of electron saturation velocity in La-doped BaSnO_{3} thin films for a range of doping densities. Predicted saturation velocities based on a simple LO-phonon emission model using an effective LO phonon energy of 120 meV show good agreement with measurements of velocity saturation in La-doped BaSnO_{3} films.. Density-dependent saturation velocity in the range of 1.6x10^{7} cm/s reducing to 2x10^{6} cm/s is predicted for {delta}-doped BaSnO3 channels with carrier densities ranging from 10^{13} cm^{-2} to 2x10^{14} cm^{-2} respectively. These results are expected to aid the informed design of BaSnO3 as the active material for high-charge density electronic transistors.
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