Formation Of Ferroelectric Phase Research Articles

Strain as a Global Factor in Stabilizing the Ferroelectric Properties of ZrO2

AbstractSince the discovery of ferroelectricity in doped HfO2 and ZrO2 thin films over a decade ago, fluorite‐structured ferroelectric thin films have attracted much research attention due to their excellent scalability and complementary metal‐oxide semiconductor compatibility compared to conventional perovskite ferroelectric materials. Although various factors influencing the formation of the ferroelectric properties are identified, a clear understanding of the causes of the phase formation have been difficult to determine. In this work, ZrO2 films deposited by atomic layer deposition and chemical solution deposition have resulted in films with completely different structural properties. Regardless of these differences, a general relationship between strain and phase formation is established, leading to a more unified understanding of ferroelectric phase formation in undoped ZrO2 films, which can be applied to other fluorite‐structured films.

Effect of Ce doping on ferroelectric HfO2 from first-principles: Implications for ferroelectric thin films and phase regulation

In this work, the effect of Ce doping on the structure and oxygen defects of ferroelectric HfO2 is studied by first-principles calculation. According to the formation energy of Ce doping and the influence of Ce doping on the formation enthalpy of each phase, it is concluded that the concentration of Ce doping is 8–9.375 formula unit% which is most beneficial to the formation of ferroelectric orthorhombic phase. The phase transition from ferroelectric orthorhombic phase to cubic phase will occur when the doping concentration is greater than 12.5 formula unit%. The mechanism of Ce doping was also studied. From the view of electric balance, it is concluded that the existence of Ce3+ will promote the formation of oxygen vacancies in HfO2. These findings are helpful for the preparation of Ce-doped HfO2 ferroelectric thin films and deepen the understanding of the Ce doping mechanism.

Rough FTO electrode interface effect upon ferroelectric switching dynamics in Ag/P(VDF‐HFP)/FTO capacitor structures

AbstractRough FTO electrode interface effect upon the characteristic ferroelectric polarization parameters and switching dynamics in Ag/P(VDF‐HFP)/FTO junctions is systematically evaluated by varying electric field amplitude and frequency. Structural and microstructural studies confirm the ferroelectric phase formation of P(VDF‐HFP) on FTO surface. Tilted rectangular P‐E loops have been recorded in the applied fields ranging over 156.25–468.75 MV/m measured between 250 mHz and 5 Hz frequency ranges. Giant saturation of 21.7 μC/cm2 and remnant polarization of 34.9 μC/cm2 has been noted at low frequencies due to the influence of high electric field induced leakage currents. The coercive field, saturation and remnant polarization response with increase in electric field amplitude and frequency of the applied signal are well fitted with classic domain growth model proposed by Kolmogorov‐Avrami‐Ishibashi. A switching time scales of 32.2–693 ms has been observed for forward switching while for backward switching it is noted as 22.1–618.8 ms, when measured at frequencies from 5 Hz to 250 mHz. Furthermore, the tilted P‐E loops are attributed to the excessive leakage currents due to the high surface roughness of FTO bottom electrode.

Фазовые состояния твердого раствора (1-x)PbFe-=SUB=-0.5-=/SUB=-Nb-=SUB=-0.5-=/SUB=-O-=SUB=-3-=/SUB=--xPbTiO-=SUB=-3-=/SUB=-. Описание на основе многоминимумных моделей

Based on the composition of two multiminimum models, a statistical model has been developed on the basis of which the formation of tetragonal and monoclinic ferroelectric phases in a solid solution (1-x)PbFe0.5Nb0.5O3-xPbTiO3 has been investigated and described. By selecting the parameters of the model, it was possible to reproduce the diagram T(x) of this solid solution. The peculiarity of the diagram is that when approaching the concentration of x~0.1, the temperatures of the phase transitions between the tetragonal and monoclinic phases decrease sharply, turning to zero. It is shown that the disappearance of the monoclinic phase is due to the specifics of the statistical properties of the eight-minimum model describing the subsystem of octahedra with eight minima. The features of the thermodynamic properties of a solid solution in the vicinity of the morphotropic boundary between the tetragonal and monoclinic phases are also investigated

Nanocrystallite Seeding of Metastable Ferroelectric Phase Formation in Atomic Layer-Deposited Hafnia-Zirconia Alloys.

Hafnia-based ferroelectric thin films are promising for semiconductor memory and neuromorphic computing applications. Amorphous, as-deposited, thin-film binary alloys of HfO2 and ZrO2 transform to the metastable, orthorhombic ferroelectric phase during post-deposition annealing and cooling. This transformation is generally thought to involve formation of a tetragonal precursor phase that distorts into the orthorhombic phase during cooling. In this work, we systematically study the effects of atomic layer deposition (ALD) temperature on the ferroelectricity of post-deposition-annealed Hf0.5Zr0.5O2 (HZO) thin films. Seed crystallites having interplanar spacings consistent with the polar orthorhombic phase are observed by a plan-view transmission electron microscope in HZO thin films deposited at an elevated ALD temperature. After ALD under conditions that promote formation of these nanocrystallites, high-polarization (Pr > 18 μC/cm2) ferroelectric switching is observed after rapid thermal annealing (RTA) at low temperature (350 °C). These results indicate the presence of minimal non-ferroelectric phases retained in the films after RTA when the ALD process forms nanocrystalline particles that seed subsequent formation of the polar orthorhombic phase.

Wake-Up Free La-Doped HfO2-ZrO2 Ferroelectrics Achieved With an Atomic Layer-Specific Doping Technique

In this letter, wake-up free La-doped HfO2-ZrO2 (HZO) ferroelectrics are experimentally fabricated using an atomic layer-specific doping (ALSD) technique, which selectively introduces La dopants at effective locations to facilitate the formation of ferroelectric orthorhombic phase. With this technique, robust La-doped HZO ferroelectric devices that are mostly free from the undesired wake-up effect and anti-ferroelectricity were demonstrated over a large La doping range (from 2.9 to 11.5%). Moreover, large remanent polarization and good endurance were achieved at the same time (>107 cycles). The outstanding performances can be attributed to the effective stabilization of ferroelectric orthogonal phase and the suppression of tetragonal phase, through controlling of the dopants’ local environment. Thus, ALSD is an effective approach to achieve reliable, wake-up free and CMOS-compatible HZO-based ferroelectrics.

Improvement of ferroelectricity and endurance in Sr doped Hf0.5Zr0.5O2 films

The doping of Hf0.5Zr0.5O2 has attracted increasing attention because of the further regulation of structure and ferroelectric properties. Here, Sr doped Hf0.5Zr0.5O2 (Sr:HZO) ferroelectric films have been prepared by chemical solution deposition on Pt/Ti/SiO2/Si substrate, and the effect of Sr doping on the structure and ferroelectric properties of Sr:HZO films was investigated. It is observed that Sr doping can further promote the formation of ferroelectric orthorhombic phase at low content (≤0.50%), inducing the enhancement of ferroelectricity. And the optimal ferroelectricity with remanent polarization of 14.63 μC/cm2 and coercive field of 1.08 MV/cm is achieved in the 0.50% Sr doped HZO film. The decrease in leakage current density with increasing Sr content is observed, which is mainly ascribed to the reduction of grain boundaries caused by the increase of grain size. Most significantly, Sr doping induces an improvement in the endurance, and a good endurance of 109 cycles without breakdown is achieved in the 0.50% Sr doped sample. These findings indicate that Sr is a potential candidate dopant for improving the structure and ferroelectric properties of HZO films.

Independent Effects of Dopant, Oxygen Vacancy, and Specific Surface Area on Crystal Phase of HfO2 Thin Films towards General Parameters to Engineer the Ferroelectricity

Many factors have been confirmed to affect ferroelectric phase formation in HfO2-based thin films but there was still a lack of general view on describing them. This paper discusses the intrinsic parameters to stabilize the ferroelectric phase of HfO2 thin films to approach this general view by investigating the separate effects of dopant, oxygen vacancy (VO), and specific surface area on the crystal phase of the films. It is found that in addition to extensively studied dopants, the ferroelectric orthorhombic phase can also be formed in pure HfO2 films by only introducing sufficient VO independently, and it is also formable by only increasing the specific surface area. By analyzing the common physics behind these factors, it is found that orthorhombic phase formation is universally related to strain in all the above cases with a given temperature. To get a general view, a physical model is established to describe how the strain influences ferroelectric phase formation during the fabrication of HfO2-based films based on thermodynamic and kinetics analysis.

Influence of the Degree of Phase Transition Diffuseness on the Depolarization Temperature in Relaxors of Different Types

The relationship between the temperatures of depolarization (Td) and morphotropic phase transition (TF-R) in crystalline relaxor solid solutions of various types, such as PbMg1/3Nb2/3O3-29PbTiO3 (PMN-29PT), PbZn1/3Nb2/3O3-9PbTiO3 (PZN-9PT) and NaBi1/2Ti1/2O3-xBaTiO3 (x=5,7.5%) (NBT-xBT) has been studied. For this purpose, dielectric measurements of polarized samples were carried out, and the process of induction of the ferroelectric phase in an electric field applied below the TF-R temperature was also studied. It was found that the structure of the low-temperature phases in these compounds is different, which leads to significant differences not only in the induction of the ferroelectric phase, but also to different relative positions of the temperatures Td and TF-R. In PMN-29PT, the formation of ferroelectric phases is preceded by some delay time, which is one of the hallmarks of a non-ergodic glassy phase, and in this case the temperatures Td and TF-R coincide. In PZN-9PT and NBT-5BT, the ferroelectric phase is induced immediately after the field is applied without a delay time, which indicates that below the TF-R temperature, the non-ergodic glassy phase does not appear, and the temperatures Td and TF-R do not coincide in them. The results obtained are discussed from the point of view of different degrees of diffuseness of the phase transition and different sizes of the polar regions. It is suggested that the coincidence of temperatures Td and TF-R is a consequence of the non-ergodic glassy phase and the small sizes of the polar regions. Keywords: relaxors, phase transitions, degree of smearing, depolarization temperature.

Induced phase transition in monocrystalline solids solutions PbMg-=SUB=-1/3-=/SUB=-Nb-=SUB=-2/3-=/SUB=-O-=SUB=-3-=/SUB=--29PbTiO-=SUB=-3-=/SUB=- and PbZn-=SUB=-1/3-=/SUB=-Nb-=SUB=-2/3-=/SUB=-O-=SUB=-3-=/SUB=--9PbTiO-=SUB=-3-=/SUB=-: similarity and difference

The kinetics of the induced phase transition in single-crystal relaxor solid solutions PbMg1/3Nb2/3O3-29PbTiO3 and PbZn1/3Nb2/3O3-9PbTiO3 is studied when an electric field is applied along the [001] direction. At temperatures below the temperature of the morphotropic phase transition, the changes in the dielectric constant and optical transmission in electric fields are studied. It is shown that the decrease in optical transmission with time is associated only with a change in the sizes of nanoregions during the phase transition. It was found that the induced phase transition proceeds differently in these crystals. In PMN-29PT crystals, the formation of ferroelectric phases and the rapid establishment of macroscopic polarization are preceded by a certain delay time, while in PZN-9PT crystals, the ferroelectric phase is induced immediately after the application of the field without a delay time. The results obtained are explained by the different structures of the low-temperature phases in these compounds. Keywords: ferroelectricity, relaxors, induced phase transition.

Влияние степени размытия фазового перехода на температуру деполяризации в релаксорах разного типа

The relationship between the temperatures of depolarization (Td) and morphotropic phase transition (TF-R) in crystalline relaxor solid solutions of various types, such as PbMg1/3Nb2/3O3-29PbTiO3 (PMN-29PT), PbZn1/3Nb2/3O3-9PbTiO3 (PZN- 9PT) and NaBi1/2Ti1/2O3-xBaTiO3 (x=5.7.5%) (NBT-xBT) has been studied. For this purpose, dielectric measurements of polarized samples were carried out, and the process of induction of the ferroelectric phase in an electric field applied below the TF-R temperature was also studied. It was found that the structure of the low-temperature phases in these compounds is different, which leads to significant differences not only in the induction of the ferroelectric phase, but also to different relative positions of the temperatures Td and TF-R. In PMN-29PT, the formation of ferroelectric phases is preceded by some delay time, which is one of the hallmarks of a non-ergodic glassy phase, and in this case the temperatures Td and TF-R coincide. In PZN-9PT and NBT-5BT, the ferroelectric phase is induced immediately after the field is applied without a delay time, which indicates that below the TF-R temperature, the non-ergodic glassy phase does not appear, and the temperatures Td and TF-R do not coincide in them. The results obtained are discussed from the point of view of different degrees of diffuseness of the phase transition and different sizes of the polar regions. It is suggested that the coincidence of temperatures Td and TF-R is a consequence of the non-ergodic glassy phase and the small sizes of the polar regions.

Review of the mechanism for Ferroelectric Phase Formation in Fluorite-structure Oxide

Review of the mechanism for Ferroelectric Phase Formation in Fluorite-structure Oxide

Impacts of surface nitridation on crystalline ferroelectric phase of Hf1-xZrxO2 and ferroelectric FET performance

This paper presents an approach to enhance Hf0.5Zr0.5O2 (HZO) ferroelectric orthorhombic phase (O-phase) formation via in situ NH3 plasma treatment. High-resolution non-disruptive hard x-ray photoelectron spectroscopy confirmed that O-phase formation can be enhanced by suppressed interfacial diffusion between HZO and the top TiN electrode. Additional N-bonding facilitated by NH3 treatment was shown to suppress the interaction between TiN and HZO, thereby reducing the formation of oxygen vacancies within HZO. It was shown to improve the reliability and ferroelectric performance (examined by the leakage current and positive-up-negative-down measurements) of HZO devices. After cyclic operations, NH3-treated ferroelectric FETs (FeFETs) exhibited stable transfer characteristics and memory windows, whereas untreated devices presented unstable behaviors. Our results demonstrate the efficacy of the proposed in situ NH3-treatment scheme in enhancing the stability of HZO-based FeFETs.

Effect of Annealing Temperature on Ferroelectric Properties of ALD Deposited TiN/Hzo/TiN Capacitor

In this work, we demonstrated the effect of annealing temperature (400℃- 600℃) on ferroelectric properties and reliability of ALD deposited TiN/HZO/TiN metal-ferroelectric-metal (MFM) capacitor stack. The thickness (9-nm) of HZO ferroelectric layer and its interface with electrodes were revealed by transmission electron microscope. The formation of ferroelectric phase for HZO annealed at different temperature were investigated by grazing incidence X-ray diffraction.The sample annealed at 600℃ shows high remanent polarization (2Pr) of 52.9 μC/cm2 and excellent endurance performances with higher than 1011 cycles at 3 V without breakdown. The time-dependent dielectric breakdown (TDDB) also indicated that samples with the higher annealing temperature exhibited better tBD than the samples with the lower annealing temperature. It is suggested that higher annealing temperature can enhance the crystalline quality as well as interface in the ALD deposited TiN/HZO/TiN capacitor . Figure 1

Ferroelectric phase transitions induced by a strain gradient

In perovskite oxide ferroelectrics, gradients of lattice strain are known to induce nanoscale topological structures, leading to novel or enhanced functionality. Here, we experimentally detect and theoretically analyze thickness distribution of structural properties in epitaxial ${\mathrm{Pb}}_{0.5}{\mathrm{Sr}}_{0.5}\mathrm{Ti}{\mathrm{O}}_{3}$ films grown on (001) $\mathrm{SrTi}{\mathrm{O}}_{3}$ substrates. We show that the relaxation of substrate-imposed stress produces a strain gradient, which leads to the formation of distinct ferroelectric phases as a function of distance from the film-substrate interface within the same film. Charge carriers trapped at phase boundaries stabilize the induced phases and manifest themselves under electric field. Crosstalk between the phases, where polarization may rotate in one phase and invert in the other one, opens perspectives for advanced ferroelectric thin film devices.

Impact of Wet Annealing on Ferroelectric Phase Formation and Phase Transition of HfO2–ZrO2 System

Wet annealing of the ZrO2 thin film can promote martensitic phase transition, leading to the formation of the ferroelectric orthorhombic (o-) phase. However, the present remanent polarization does ...

Influence of High-Pressure Annealing Conditions on Ferroelectric and Interfacial Properties of Zr-Rich HfₓZr₁₋ₓO₂Capacitors

In this study, we have carried out an in-depth analysis on the role of high-pressure annealing (HPA) conditions on ferroelectricity as well as the interfacial property of Hf <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> Zr <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">1-x</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (HZO) capacitors in metal-ferroelectric-metal (MFM) structure. Unlike conventional 1:1 HZO films, HZO demonstrates the highest ferroelectricity at 1:3 Hf:Zr ratio in HPA and a significantly higher maximum remanent polarization ( P <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</sub> ) of 31 μC/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> was achieved as compared to 19 μC/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> obtained in rapid thermal annealing (RTA) (HZO [1:1]). To understand the influence of HPA conditions, HZO [1:3] capacitors are annealed at various temperatures (300 °C, 400 °C, 500 °C, and 600 °C) and pressures (1, 50, and 200 atm). Ferroelectricity in HZO is found to enhance with increasing HPA temperature or pressure due to higher ferroelectric phase formation as revealed by grazing incidence X-ray diffractometer (GIXRD) analysis. Transient pulse switching measurement suggests the reduction in the effective thickness of the interfacial nonferroelectric film at a high HPA temperature or pressure which was also validated by impedance analysis. Further, impedance analysis reveals a reduction in the number of oxygen vacancy defects with increasing annealing temperature or pressure implying a phase transition from the tetragonal phase of nonferroelectric layer to the ferroelectric orthorhombic phase. In addition, excellent endurance property till 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">9</sup> cycles with reduced wake-up effect was observed in HZO [1:3] capacitors with increasing the HPA temperature, while higher annealing pressure is found to increase P <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</sub> without affecting its endurance property. The results obtained herein can be of significant scientific importance, especially to achieve enhanced ferroelectric property with reduced wake-up effect in Zr-rich HZO ferroelectrics.

In Situ Characterization of Ferroelectric HfO2 During Rapid Thermal Annealing

Thermal annealing is critical in governing the phase distribution, and ultimately the electrical properties, of ferroelectric hafnium oxide films. In particular, rapid thermal annealing (RTA) has been shown to favor the formation of ferroelectric crystal phases, but the dynamic behavior of the film over the course of the anneal is not well understood. Herein, synchrotron X‐ray diffraction is used to characterize the phase distribution of HfO2 films deposited by atomic layer deposition (ALD) in situ during RTA, revealing complex phase transformations occurring on the scale of seconds. All samples investigated here transform into a nonmonoclinic phase, which is required for ferroelectric films. However, this phase often converts into the more stable monoclinic phase as annealing proceeds. The kinetic barrier to the transformation to the monoclinic phase during heating is higher than 1 eV f.u.−1 The initial crystallization into the ferroelectric phase and relatively high barrier to transformation to the nonferroelectric phase suggests that careful control of the thermal annealing profile can greatly increase the ferroelectric fraction of the film. By using a fast ramp rate and a short annealing time above the ferroelectric crystallization temperature, the remanent polarization of a pure HfO2 film can be increased more than twofold.

Индуцированный фазовый переход в монокристаллических твердых растворах PbMg-=SUB=-1/3-=/SUB=-Nb-=SUB=-2/3-=/SUB=-O-=SUB=-3-=/SUB=--29PbTiO-=SUB=-3-=/SUB=- и PbZn-=SUB=-1/3-=/SUB=-Nb-=SUB=-2/3-=/SUB=-O-=SUB=-3-=/SUB=--9PbTiO-=SUB=-3-=/SUB=-: сходство и различие

The kinetics of the induced phase transition in single-crystal relaxor solid solutions PbMg1 / 3Nb2 / 3O3-29PbTiO3 and PbZn1 / 3Nb2 / 3O3-9PbTiO3 is studied when an electric field is applied along the [001] direction. At temperatures below the temperature of the morphotropic phase transition, the changes in the dielectric constant and optical transmission in electric fields are studied. It is shown that the decrease in optical transmission with time is associated only with a change in the sizes of nanoregions during the phase transition. It was found that the induced phase transition proceeds differently in these crystals. In PMN-29PT crystals, the formation of ferroelectric phases and the rapid establishment of macroscopic polarization are preceded by a certain delay time, while in PZN-9PT crystals, the ferroelectric phase is induced immediately after the application of the field without a delay time. The results obtained are explained by the different structures of the low-temperature phases in these compounds. Key words: ferroelectricity, relaxors, induced phase transition.

Interplay between oxygen defects and dopants: effect on structure and performance of HfO2-based ferroelectrics

A review on ferroelectric phase formation and reliability in HfO2-based thin films and semiconductor devices.