Polarization rotation mechanism for ultrahigh electromechanical response in single-crystal piezoelectrics
TL;DR: It is shown that a large piezoelectric response can be driven by polarization rotation induced by an external electric field, and the computations suggest how to design materials with better performance, and may stimulate further interest in the fundamental theory of dielectric systems in finite electric fields.
Abstract: Piezoelectric materials, which convert mechanical to electrical energy (and vice versa), are crucial in medical imaging, telecommunication and ultrasonic devices. A new generation of single-crystal materials, such as Pb(Zn1/3Nb2/3)O3-PbTiO3 (PZN-PT) and Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), exhibit a piezoelectric effect that is ten times larger than conventional ceramics, and may revolutionize these applications. However, the mechanism underlying the ultrahigh performance of these new materials-and consequently the possibilities for further improvements-are not at present clear. Here we report a first-principles study of the ferroelectric perovskite, BaTiO3, which is similar to single-crystal PZN-PT but is a simpler system to analyse. We show that a large piezoelectric response can be driven by polarization rotation induced by an external electric field. Our computations suggest how to design materials with better performance, and may stimulate further interest in the fundamental theory of dielectric systems in finite electric fields.
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TL;DR: It is predicted that the single-crystal form of the MPB composition of the present system may reach a giant d(33) = 1500-2000 pC/N, which may provide a new recipe for designing highly piezoelectric materials (both Pb-free and P b-containing) by searching MPBs starting from a TCP.
Abstract: We report a non-Pb piezoelectric ceramic system Ba(Ti(0.8)Zr(0.2))O(3)-(Ba(0.7)Ca(0.3))TiO(3) which shows a surprisingly high piezoelectric coefficient of d(33) approximately 620 pC/N at optimal composition. Its phase diagram shows a morphotropic phase boundary (MPB) starting from a tricritical triple point of a cubic paraelectric phase (C), ferroelectric rhombohedral (R), and tetragonal (T) phases. The high piezoelectricity of the MPB compositions stems from the composition proximity of the MPB to the tricritical triple point, which leads to a nearly vanishing polarization anisotropy and thus facilitates polarization rotation between 001T and 111R states. We predict that the single-crystal form of the MPB composition of the present system may reach a giant d(33) = 1500-2000 pC/N. Our work may provide a new recipe for designing highly piezoelectric materials (both Pb-free and Pb-containing) by searching MPBs starting from a TCP.
2,197 citations
TL;DR: In this article, the authors introduce the current state of development in the application of ferroelectric thin films for electronic devices and discuss the physics relevant for the performance and failure of these devices.
Abstract: This review covers important advances in recent years in the physics of thin-film ferroelectric oxides, the strongest emphasis being on those aspects particular to ferroelectrics in thin-film form. The authors introduce the current state of development in the application of ferroelectric thin films for electronic devices and discuss the physics relevant for the performance and failure of these devices. Following this the review covers the enormous progress that has been made in the first-principles computational approach to understanding ferroelectrics. The authors then discuss in detail the important role that strain plays in determining the properties of epitaxial thin ferroelectric films. Finally, this review ends with a look at the emerging possibilities for nanoscale ferroelectrics, with particular emphasis on ferroelectrics in nonconventional nanoscale geometries.
1,908 citations
TL;DR: It is shown that, contrary to current thought, BaTiO3 thin films between two metallic SrRuO3 electrodes in short circuit lose their ferro electric properties below a critical thickness of about six unit cells, suggesting the existence of a lower limit for the thickness of useful ferroelectric layers in electronic devices.
Abstract: The integration of ferroelectric oxide films into microelectronic devices, combined with the size reduction constraints imposed by the semiconductor industry, have revived interest in the old question concerning the possible existence of a critical thickness for ferroelectricity. Current experimental techniques have allowed the detection of ferroelectricity in perovskite films down to a thickness of 40 A (ten unit cells), ref. 3. Recent atomistic simulations have confirmed the possibility of retaining the ferroelectric ground state at ultralow thicknesses, and suggest the absence of a critical size. Here we report first-principles calculations on a realistic ferroelectric-electrode interface. We show that, contrary to current thought, BaTiO3 thin films between two metallic SrRuO3 electrodes in short circuit lose their ferroelectric properties below a critical thickness of about six unit cells (approximately 24 A). A depolarizing electrostatic field, caused by dipoles at the ferroelectric-metal interfaces, is the reason for the disappearance of the ferroelectric instability. Our results suggest the existence of a lower limit for the thickness of useful ferroelectric layers in electronic devices.
1,355 citations
Cites background from "Polarization rotation mechanism for..."
...In the presence of the field b d , the energy E of the thin film can be expressed a...
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TL;DR: In this article, a morphotropic phase boundary between orthorhombic and tetragonal phases is found in the composition range 0.05
Abstract: Lead-free piezoelectric ceramics (1−x)(Na0.5K0.5)NbO3–xLiNbO3 {[Lix(Na0.5K0.5)1−x]NbO3} (x=0.04–0.20) have been synthesized by an ordinary sintering technique. The materials with perovskite structure is orthorhombic phase at x⩽0.05 and becomes tetragonal phase at x⩾0.07, a phase K3Li2Nb5O15 with tetragonal tungsten bronze structure begins to appear at x=0.08 and becomes dominant with increasing the content of LiNbO3. A morphotropic phase boundary between orthorhombic and tetragonal phases is found in the composition range 0.05
1,354 citations
1,175 citations
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Book•
06 Oct 1977
TL;DR: In this paper, the theory of ferroelectricity in terms of soft modes and lattice dynamics is developed and modern techniques of measurement, including X-ray, optic, and neutron scattering, infra-red absorption, and magnetic resonance.
Abstract: The book develops the modern theory of ferroelectricity in terms of soft modes and lattice dynamics and also describes modern techniques of measurement, including X-ray, optic, and neutron scattering, infra-red absorption, and magnetic resonance. It includes a discussion of the related phenomena of antiferroelectricity, pyroelectricity, and ferroelasticity and seconds on domains, thin films, ceramics, and polymers, leading on to a comprehensive survey of potential and actual device capabilities for pyroelectric detection, memories, display, and modulation. It should provide an authoritative account for those engaged in research or graduate ferroelectric or pyroelectric devices.
4,931 citations
Additional excerpts
...gif" NDATA ITEM> ]> Piezoelectric materials, which convert mechanical to electrical energy (and vice versa), are crucial in medical imaging, telecommunication and ultrasonic device...
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TL;DR: In this article, the piezoelectric properties of relaxor based ferroelectric single crystals, such as Pb(Zn1/3Nb2/3)O3 and PbTiO3, were investigated for electromechanical actuators.
Abstract: The piezoelectric properties of relaxor based ferroelectric single crystals, such as Pb(Zn1/3Nb2/3)O3–PbTiO3 and Pb(Mg1/3Nb2/3)O3–PbTiO3 were investigated for electromechanical actuators. In contrast to polycrystalline materials such as Pb(Zr,Ti)O3, morphotropic phase boundary compositions were not essential for high piezoelectric strain. Piezoelectric coefficients (d33’s)>2500 pC/N and subsequent strain levels up to >0.6% with minimal hysteresis were observed. Crystallographically, high strains are achieved for 〈001〉 oriented rhombohedral crystals, although 〈111〉 is the polar direction. Ultrahigh strain levels up to 1.7%, an order of magnitude larger than those available from conventional piezoelectric and electrostrictive ceramics, could be achieved being related to an E-field induced phase transformation. High electromechanical coupling (k33)>90% and low dielectric loss <1%, along with large strain make these crystals promising candidates for high performance solid state actuators.
3,766 citations
"Polarization rotation mechanism for..." refers background in this paper
...Our calculations further suggest that, in addition to a rhombohedral phase at zero ®eld and a high strain level in the tetragonal phase, good materials need to have: (1) a ̄at energy surface (that is, soft force constants for ferroelectric displacements) near the rhombohedral phase, so that a small ®eld will cause a large change of polarization angle; (2) large effective charges (thus a large c-axis polarization variation to be coupled with electric ®eld during polarization rotation); and (3) strong coupling between the internal degrees of freedom and strain....
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TL;DR: It is shown that physically $\ensuremath{\Delta}P can be interpreted as a displacement of the center of charge of the Wannier functions.
Abstract: We consider the change in polarization \ensuremath{\Delta}P which occurs upon making an adiabatic change in the Kohn-Sham Hamiltonian of the solid. A simple expression for \ensuremath{\Delta}P is derived in terms of the valence-band wave functions of the initial and final Hamiltonians. We show that physically \ensuremath{\Delta}P can be interpreted as a displacement of the center of charge of the Wannier functions. The formulation is successfully applied to compute the piezoelectric tensor of GaAs in a first-principles pseudopotential calculation.
3,136 citations
TL;DR: In this paper, the authors report results of electronic-structure calculations on two classic examples of ferroelectric perovskites, BaTiO3 and PbTiO2, and demonstrate that hybridization between the titanium 3d states and the oxygen 2p states is essential for ferroelectivity.
Abstract: FERROELECTRIC materials are characterized by a switchable macroscopic polarization. Most technologically important ferroelectrics are oxides with a perovskite structure. The origin of their ferroelectric behaviour is unclear, however, and there is incomplete understanding of why similar, but chemically different, perovskites should display very different ferroelectric behaviour. The great sensitivity of ferroelectrics to chemistry, defects, electrical boundary conditions and pressure arises from a delicate balance between long-range Coulomb forces (which favour the ferroelectric state) and short-range repulsions (which favour the nonpolar cubic structure). To model the transition accurately, total-energy techniques are required which incorporate the effects of charge distortion and covalency. Here I report results of electronic-structure calculations on two classic examples of ferroelectric perovskites, BaTiO3 and PbTiO3, and demonstrate that hybridization between the titanium 3d states and the oxygen 2p states is essential for ferroelectricity. The different ferroelectric phase behaviour of the two materials is also clear: in PbTiO3, the lead and oxygen states hybridize, leading to a large strain that stabilizes the tetragonal phase, whereas in BaTiO3 the interaction between barium and oxygen is completely ionic, favouring a rhombohedral structure.
2,417 citations
TL;DR: In this paper, King-Smith and Vanderbilt developed a complete theory in which the polarization difference between any two crystal states in a null electric field takes the form of a geometric quantum phase.
Abstract: The macroscopic electric polarization of a crystal is often defined as the dipole of a unit cell. In fact, such a dipole moment is ill defined, and the above definition is incorrect. Looking more closely, the quantity generally measured is differential polarization, defined with respect to a "reference state" of the same material. Such differential polarizations include either derivatives of the polarization (dielectric permittivity, Born effective charges, piezoelectricity, pyroelectricity) or finite differences (ferroelectricity). On the theoretical side, the differential concept is basic as well. Owing to continuity, a polarization difference is equivalent to a macroscopic current, which is directly accessible to the theory as a bulk property. Polarization is a quantum phenomenon and cannot be treated with a classical model, particularly whenever delocalized valence electrons are present in the dielectric. In a quantum picture, the current is basically a property of the phase of the wave functions, as opposed to the charge, which is a property of their modulus. An elegant and complete theory has recently been developed by King-Smith and Vanderbilt, in which the polarization difference between any two crystal states---in a null electric field---takes the form of a geometric quantum phase. The author gives a comprehensive account of this theory, which is relevant for dealing with transverse-optic phonons, piezoelectricity, and ferroelectricity. Its relation to the established concepts of linear-response theory is also discussed. Within the geometric phase approach, the relevant polarization difference occurs as the circuit integral of a Berry connection (or "vector potential"), while the corresponding curvature (or "magnetic field") provides the macroscopic linear response.
1,867 citations