skip to main content


Title: A Janovec‐Kay‐Dunn‐Like Behavior at Thickness Scaling in Ultra‐Thin Antiferroelectric ZrO 2 Films
Abstract

Originally based on phenomenological observations, the Janovec–Kay–Dunn (JKD) scaling law has been historically used to describe the dependence of the ferroelectric coercive fields (Ec) on a critical length scale of the material, wherein the film thickness (t) is considered the length scale, andEct−2/3. Here, for the first time, a JKD‐type scaling behavior is reported in an antiferroelectric material, using the ultra‐thin films of prototypical flourite‐structure binary oxide, zirconia. In these films, a decrease in the ZrO2layer thickness from 20 nm to 5.4 nm leads to an increase in critical fields for both nonpolar‐to‐polar (Ea), and polar‐to‐nonpolar (Ef) transitions, accompanied by a decrease in the average crystallite size, and an increase in the tetragonal distortion of the non‐polarP42/nmcground state structure. Notably, the ‐2/3 power law as in the JKD law holds when average crystallite size (d), measured from glancing‐incident X‐ray diffraction, is considered as the critical length scale—i.e.,Ea,Efd−2/3. First principles calculations suggest that the increase of tetragonality in thinner films contributes to an increase of the energy barrier for the transition from the non‐polar tetragonal ground state to the field‐induced polar orthorhombic phase, and in turn, an increase inEacritical fields. These results suggest a de‐stabilization of the ferroelectric phase with a decreasing thickness in antiferroelectric ZrO2, which is contrary to the observations in its fluorite‐structure ferroelectric counterparts. With the recent interests in utilizing antiferroelectricity for advanced semiconductor applications, our fundamental exposition of the thickness dependence of functional responses therein can accelerate the development of miniaturized, antiferroelectric electronic memory elements for the complementary metal‐oxide‐semiconductor based high‐volume manufacturing platforms.

 
more » « less
NSF-PAR ID:
10360111
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Electronic Materials
Volume:
7
Issue:
11
ISSN:
2199-160X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The unique nonlinear dielectric properties of antiferroelectric (AFE) oxides are promising for advancements in solid state supercapacitor, actuator, and memory technologies. AFE behavior in high‐k ZrO2is of particular technological interest, but the origin of antiferroelectricity in ZrO2remains questionable. The theory of reversible electric field‐induced phase transitions between the nonpolar P42/nmc tetragonal phase and the polarPca21orthorhombic phase is experimentally tested with local structural and electromechanical characterization of AFE ZrO2thin films. Piezoresponse force microscopy identifies signature evidence of a field‐induced phase transition. A significant size effect in AFE ZrO2is experimentally observed as film thickness is scaled down from 14.7 to 4.3 nm. The size effect is explained by modifications to the phase transition energy barrier heights ranging from 0.6 to 7.6 meV f.u−1depending on crystallite size and in‐plane compressive strain with decreasing ZrO2film thickness. Using the size effect, it is possible to double the energy storage density in ZrO2from 20 J cm−3to greater than 40 J cm−3, thus highlighting a feasible route for superior performance in AFE fluorite supercapacitors.

     
    more » « less
  2. Abstract

    Knowledge about phase transitions in doped HfO2and ZrO2‐based films is crucial for developing future ferroelectric devices. These devices should perform in ambient temperature ranges with no degradation of device performance. Here, the phase transition from the polar orthorhombic to the nonpolar tetragonal phase in thin films is of significant interest. Detailed electrical and structural characterization is performed on 10 nm mixed HfxZr1‐xO2binary oxides with different ZrO2in HfO2and small changes in oxygen content. Both dopant and oxygen content directly impact the phase transition temperature between the polar and nonpolar phase. A first‐order phase transition with thermal hysteresis is observed from the nonpolar to the polar phase with a maximum in the dielectric constant. The observed phase transition temperatures confirm trends as obtained by DFT calculations. Based on the outcome of the measurements, the classification of the ferroelectric material is discussed.

     
    more » « less
  3. Abstract

    The hafnate perovskites PbHfO3(antiferroelectric) and SrHfO3(“potential” ferroelectric) are studied as epitaxial thin films on SrTiO3(001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb1−xSrxHfO3system. The resulting (240)‐oriented PbHfO3(Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm−2at 1.6 MV cm−1, weak‐field dielectric constant ≈186 at 298 K, and an antiferroelectric‐to‐paraelectric phase transition at ≈518 K. (002)‐oriented SrHfO3films exhibited neither ferroelectric behavior nor evidence of a polarP4mmphase . Instead, the SrHfO3films exhibited a weak‐field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77–623 K) and electric field (–3 to 3 MV cm−1). While the lack of ferroelectric order in SrHfO3removes the potential for MPB, structural and property evolution of the Pb1−xSrxHfO3(0 ≤x < 1) system is explored. Strontium alloying increased the electric‐breakdown strength (EB) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (Ur) and efficiency (η). The composition, Pb0.5Sr0.5HfO3produced the best combination ofEB = 5.12 ± 0.5 MV cm−1,Ur = 77 ± 5 J cm−3, and η = 97 ± 2%, well out‐performing PbHfO3and other antiferroelectric oxides.

     
    more » « less
  4. Abstract

    The recently discovered ferroelectric nematic (NF) liquid crystals (LCs) with over 0.04 C m−2ferroelectric polarization and 104relative dielectric constants, coupled with sub‐millisecond switching, offer potential applications in high‐power super capacitors and low voltage driven fast electro‐optical devices. This paper presents electrical, optical, and electro‐optical studies of a ferroelectric nematic LC material doped with commercially available chiral dopants. While theNFphase of the undoped LC is only monotropic, the chiralNFphase is enantiotropic, indicating a chirality induced stabilization of the polar nematic order. Compared to undopedNFmaterial, a remarkable improvement of the electro‐optical switching time is demonstrated in the chiral doped materials. The color of the chiral mixtures that exhibit a selective reflection of visible light in the chiralNFphase, can be reversibly tuned by 0.02–0.1 V µm−1 in‐plane electric fields, which are much smaller than typically required in full‐color cholesteric LC displays and do not require complicated driving scheme. The fast switchable reflection color at low fields has potential applications for LC displays without backlight, smart windows, shutters, and e‐papers.

     
    more » « less
  5. There is a strong drive behind the quest for thin-film materials that are oxygen-free and polar. Oxygen hinders the integration of ferroelectric oxides with semiconductors, which affects efforts to develop nonvolatile memory—that is, a memory that can sustain its information without power. Ideally, one would use single-crystalline perovskite films to construct these devices so that the polarization can be maximized. However, when depositing crystalline polar perovskite oxides onto silicon or germanium, a nonpolar oxide buffer layer ( 1 ) or a native oxide layer ( 2 ) can be present at the interface, compromising device performance. A nitrogen-based perovskite may overcome this limitation ( 3 ). On page 1488 of this issue, Talley et al. ( 4 ) report the synthesis of lanthanum tungsten nitride (LaWN 3 ) thin films, which marks the first demonstration of polar nitride perovskite. This may lead to oxygen-free integration of functional perovskite on a semiconductor platform. 
    more » « less