Insights into electrical characteristics of silicon doped hafnium oxide ferroelectric thin films
TL;DR: In this article, metal-ferroelectric-metal capacitors with Si:HfO2 thin films as ferroelectric material and TiN as electrodes have been characterized with respect to capacitance and current density as functions of temperature and applied voltage.
Abstract: Silicon doped hafnium oxide thin films were recently discovered to exhibit ferroelectricity. In the present study, metal-ferroelectric-metal capacitors with Si:HfO2 thin films as ferroelectric material and TiN as electrodes have been characterized with respect to capacitance and current density as functions of temperature and applied voltage. Polarity asymmetry of the frequency dependent coercive field was explained by interfacial effects. No ferroelectric-paraelectric phase transition was observed at temperatures up to 478 K. Clear distinctions between current evolutions with or without polarization switching were correlated to the time competition between the measurement and the response of relaxation mechanisms.
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TL;DR: The coupling of electric and thermal properties of the antiferroelectric thin films is expected to be useful for various applications, including energy harvesting/storage, solid-state-cooling, and infrared sensors.
Abstract: The recent progress in ferroelectricity and antiferroelectricity in HfO2-based thin films is reported. Most ferroelectric thin film research focuses on perovskite structure materials, such as Pb(Zr,Ti)O3, BaTiO3, and SrBi2Ta2O9, which are considered to be feasible candidate materials for non-volatile semiconductor memory devices. However, these conventional ferroelectrics suffer from various problems including poor Si-compatibility, environmental issues related to Pb, large physical thickness, low resistance to hydrogen, and small bandgap. In 2011, ferroelectricity in Si-doped HfO2 thin films was first reported. Various dopants, such as Si, Zr, Al, Y, Gd, Sr, and La can induce ferro-electricity or antiferroelectricity in thin HfO2 films. They have large remanent polarization of up to 45 μC cm(-2), and their coercive field (≈1-2 MV cm(-1)) is larger than conventional ferroelectric films by approximately one order of magnitude. Furthermore, they can be extremely thin ( 5 eV). These differences are believed to overcome the barriers of conventional ferroelectrics in memory applications, including ferroelectric field-effect-transistors and three-dimensional capacitors. Moreover, the coupling of electric and thermal properties of the antiferroelectric thin films is expected to be useful for various applications, including energy harvesting/storage, solid-state-cooling, and infrared sensors.
740 citations
TL;DR: In this paper, the structural, thermal, and dielectric properties of the ferroelectric phase of HfO2, ZrO2 and Hf0.5O2 are investigated with carefully validated density functional computations.
Abstract: The structural, thermal, and dielectric properties of the ferroelectric phase of HfO2, ZrO2, and Hf0.5Zr0.5O2 (HZO) are investigated with carefully validated density functional computations. We find that the free bulk energy of the ferroelectric orthorhombic Pca21 phase is unfavorable compared to the monoclinic P21/c and the orthorhombic Pbca phase for all investigated stoichiometries in the Hf1−xZrxO2 system. To explain the existence of the ferroelectric phase in nanoscale thin films, we explore the Gibbs/Helmholtz free energies as a function of stress and film strain and find them unlikely to become minimal in HZO films for technological relevant conditions. To assess the contribution of surface energy to the phase stability, we parameterize a model, interpolating between existing data, and find the Helmholtz free energy of ferroelectric grains minimal for a range of size and stoichiometry. From the model, we predict undoped HfO2 to be ferroelectric for a grain size of about 4 nm and epitaxial HZO below 5 nm. Furthermore, we calculate the strength of an applied electric field necessary to cause the antiferroelectric phase transformation in ZrO2 from the P42/nmc phase as 1 MV/cm in agreement with experimental data, explaining the mechanism of field induced phase transformation.
528 citations
TL;DR: In this article, the structural, thermal, and dielectric properties of the ferroelectric phase of HfO$_2, ZrO_2$ and Hf$_{0.5}$ Zr$_{1-\chi}$ O$-2$ (HZO) are investigated with carefully validated density functional computations.
Abstract: The structural, thermal, and dielectric properties of the ferroelectric phase of HfO$_2$, ZrO$_2$ and Hf$_{0.5}$ Zr$_{0.5}$ O$_2$ (HZO) are investigated with carefully validated density functional computations. We find, that the free bulk energy of the ferroelectric orthorhombic Pca2$_{1}$ phase is unfavorable compared to the monoclinic P2$_{1}$/c and the orthorhombic Pbca phase for all investigated stoichiometries in the Hf$_{\chi}$Zr$_{1-\chi}$O$_2$ system. To explain the existence of the ferroelectric phase in nanoscale thin films we explore the Gibbs / Helmholtz free energies as a function of stress and film strain and find them unlikely to become minimal in HZO films for technological relevant conditions. To assess the contribution of surface energy to the phase stability we parameterize a model, interpolating between existing data, and find the Helmholtz free energy of ferroelectric grains minimal for a range of size and stoichiometry. From the model we predict undoped HfO$_2$ to be ferroelectric for a grain size of about 4 nm and epitaxial HZO below 5 nm. Furthermore we calculate the strength of an applied electric field necessary to cause the antiferroelectric phase transformation in ZrO$_2$ from the P4$_2$/nmc phase as 1 MV/cm in agreement with experimental data, explaining the mechanism of field induced phase transformation.
432 citations
TL;DR: The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions in this paper.
Abstract: The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions Metal-ferroelectric-metal capacitors containing Gd:HfO2 showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants A qualitative model describing the influence of basic process parameters on the crystal structure of HfO2 was proposed The influence of different structural parameters on the field cycling behavior was examined This revealed the wake-up effect in doped HfO2 to be dominated by interface induced effects, rather than a field induced phase transition TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO2 compared to TiN electrodes, yielding a Pr of up to 35 μC/cm2 This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:Hf
404 citations
TL;DR: In this article, the switching stability of a Si-doped HfO2 film under bipolar pulsed-field operation was investigated and a de-pinning of domains due to reduction of the defect concentration at bottom electrode interface was suggested as the origin of the wake-up.
Abstract: Hafnium oxide based ferroelectric thin films have shown potential as a promising alternative material for non-volatile memory applications This work reports the switching stability of a Si-doped HfO2 film under bipolar pulsed-field operation High field cycling causes a “wake-up” in virgin “pinched” polarization hysteresis loops, demonstrated by an enhancement in remanent polarization and a shift of negative coercive voltage The rate of wake-up is accelerated by either reducing the frequency or increasing the amplitude of the cycling field We suggest de-pinning of domains due to reduction of the defect concentration at bottom electrode interface as origin of the wake-up
297 citations
References
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TL;DR: Ferroelectric, dielectric, and piezoelectric properties of ferroelectric thin films and ceramics are reviewed with the aim of providing an insight into different processes which may affect the behaviour of Ferroelectric devices.
Abstract: Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and ceramics are reviewed with the aim of providing an insight into different processes which may affect the behaviour of ferroelectric devices, such as ferroelectric memories and micro-electro-mechanical systems. Taking into consideration recent advances in this field, topics such as polarization switching, polarization fatigue, effects of defects, depletion layers, and depolarization fields on hysteresis loop behaviour, and contributions of domain-wall displacement to dielectric and piezoelectric properties are discussed. An introduction into dielectric, pyroelectric, piezoelectric and elastic properties of ferroelectric materials, symmetry considerations, coupling of electro-mechanical and thermal properties, and definitions of relevant ferroelectric phenomena are provided.
1,835 citations
TL;DR: An overview of the state of the art in ferroelectric thin films is presented in this paper, where the authors review applications: micro-systems' applications, applications in high frequency electronics, and memories based on Ferroelectric materials.
Abstract: An overview of the state of art in ferroelectric thin films is presented. First, we review applications: microsystems' applications, applications in high frequency electronics, and memories based on ferroelectric materials. The second section deals with materials, structure (domains, in particular), and size effects. Properties of thin films that are important for applications are then addressed: polarization reversal and properties related to the reliability of ferroelectric memories, piezoelectric nonlinearity of ferroelectric films which is relevant to microsystems' applications, and permittivity and loss in ferroelectric films-important in all applications and essential in high frequency devices. In the context of properties we also discuss nanoscale probing of ferroelectrics. Finally, we comment on two important emerging topics: multiferroic materials and ferroelectric one-dimensional nanostructures. (c) 2006 American Institute of Physics.
1,632 citations
TL;DR: In this paper, it was shown that crystalline phases with ferroelectric behavior can be formed in thin thin films of SiO2 doped hafnium oxide, which is suitable for field effect transistors and capacitors due to its excellent compatibility to silicon technology.
Abstract: We report that crystalline phases with ferroelectric behavior can be formed in thin films of SiO2 doped hafnium oxide. Films with a thickness of 10 nm and with less than 4 mol. % of SiO2 crystallize in a monoclinic/tetragonal phase mixture. We observed that the formation of the monoclinic phase is inhibited if crystallization occurs under mechanical encapsulation and an orthorhombic phase is obtained. This phase shows a distinct piezoelectric response, while polarization measurements exhibit a remanent polarization above 10 μC/cm2 at a coercive field of 1 MV/cm, suggesting that this phase is ferroelectric. Ferroelectric hafnium oxide is ideally suited for ferroelectric field effect transistors and capacitors due to its excellent compatibility to silicon technology.
1,631 citations
TL;DR: In this article, the choice of oxides, their structural and metallurgical behaviour, atomic diffusion, their deposition, interface structure and reactions, their electronic structure, bonding, band offsets, mobility degradation, flat band voltage shifts and electronic defects are discussed.
Abstract: The scaling of complementary metal oxide semiconductor (CMOS) transistors has led to the silicon dioxide layer used as a gate dielectric becoming so thin (1.4 nm) that its leakage current is too large. It is necessary to replace the SiO2 with a physically thicker layer of oxides of higher dielectric constant (κ) or 'high K' gate oxides such as hafnium oxide and hafnium silicate. Little was known about such oxides, and it was soon found that in many respects they have inferior electronic properties to SiO2 ,s uch as a tendency to crystallise and a high concentration of electronic defects. Intensive research is underway to develop these oxides into new high quality electronic materials. This review covers the choice of oxides, their structural and metallurgical behaviour, atomic diffusion, their deposition, interface structure and reactions, their electronic structure, bonding, band offsets, mobility degradation, flat band voltage shifts and electronic defects. The use of high K oxides in capacitors of dynamic random access memories is also covered.
1,500 citations
TL;DR: In this article, structural and electrical evidence for a ferroelectric phase in yttrium doped hafnium oxide thin films is presented, based on X-ray diffraction.
Abstract: Structural and electrical evidence for a ferroelectric phase in yttrium doped hafnium oxide thin films is presented. A doping series ranging from 2.3 to 12.3 mol% YO1.5 in HfO2 was deposited by a thermal atomic layer deposition process. Grazing incidence X-ray diffraction of the 10 nm thick films revealed an orthorhombic phase close to the stability region of the cubic phase. The potential ferroelectricity of this orthorhombic phase was confirmed by polarization hysteresis measurements on titanium nitride based metal-insulator-metal capacitors. For 5.2 mol% YO1.5 admixture the remanent polarization peaked at 24 μC/cm2 with a coercive field of about 1.2 MV/cm. Considering the availability of conformal deposition processes and CMOS-compatibility, ferroelectric Y:HfO2 implies high scaling potential for future, ferroelectric memories.
499 citations