Ulrich Böttger

Ferroelectricity in hafnium oxide thin films

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.

Ferroelectricity in Simple Binary ZrO2 and HfO2

The transition metal oxides ZrO(2) and HfO(2) as well as their solid solution are widely researched and, like most binary oxides, are expected to exhibit centrosymmetric crystal structure and therewith linear dielectric characteristics. For this reason, those oxides, even though successfully introduced into microelectronics, were never considered to be more than simple dielectrics possessing limited functionality. Here we report the discovery of a field-driven ferroelectric phase transition in pure, sub 10 nm ZrO(2) thin films and a composition- and temperature-dependent transition to a stable ferroelectric phase in the HfO(2)-ZrO(2) mixed oxide. These unusual findings are attributed to a size-driven tetragonal to orthorhombic phase transition that in thin films, similar to the anticipated tetragonal to monoclinic transition, is lowered to room temperature. A structural investigation revealed the orthorhombic phase to be of space group Pbc2(1), whose noncentrosymmetric nature is deemed responsible for the spontaneous polarization in this novel, nanoscale ferroelectrics.

Beyond von Neumann—logic operations in passive crossbar arrays alongside memory operations

The realization of logic operations within passive crossbar memory arrays is a promising approach to expand the fields of application of such architectures. Material implication was recently suggested as the basic function of memristive crossbar junctions, and single bipolar resistive switches (BRS) as well as complementary resistive switches (CRS) were shown to be capable of realizing this logical functionality. Based on a systematic analysis of the Boolean functions, we demonstrate here that 14 of 16 Boolean functions can be realized with a single BRS or CRS cell in at most three sequential cycles. Since the read-out step is independent of the logic operation steps, the result of the logic operation is directly stored to memory, making logic-in-memory applications feasible.

Ferroelectricity in yttrium-doped hafnium oxide

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.

Differentiating 180° and 90° switching of ferroelectric domains with three-dimensional piezoresponse force microscopy

Three-dimensional (3D) piezoresponse force microscopy is applied in order to differentiate 90° and 180° domain switching in PbTiO3 (PTO) thin films. The 3D domain configuration is recorded both statically, revealing the surface crystallographic orientation of PTO films on the nanometer scale, and dynamically by simultaneously mapping the in-plane and out-of-plane hysteresis loops. We show that exclusively 180° switching occurs, also switching only half of the grain volume.

Simulation of multilevel switching in electrochemical metallization memory cells

We report on a simulation model for bipolar resistive switching in cation-migration based memristive devices. The model is based on the electrochemical driven growth and dissolution of a metallic filament. The origin of multilevel switching is proposed to be direct tunneling between the growing filament and the counter electrode. An important result of our parameter simulation studies is that different materials show the same experimental multilevel behavior. Our model fully reproduces the experimental data and allows for an explanation of the transition from bipolar to nonpolar switching.

Ferroelectric Zr0.5Hf0.5O2 thin films for nonvolatile memory applications

We report the observation of ferroelectricity in capacitors based on hafnium-zirconium-oxide. Hf0.5Zr0.5O2 thin films of 7.5 to 9.5 nm thickness were found to exhibit ferroelectric polarization-voltage hysteresis loops when integrated into TiN-based metal-insulator-metal capacitors. A remnant polarization of 16 μC/cm2 and a high coercive field of 1 MV/cm were observed. Further proof for the ferroelectric nature was collected by quasi-static polarization-voltage hysteresis, small signal capacitance-voltage, and piezoelectric measurements. Data retention characteristics were evaluated by a Positive Up Negative Down pulse technique. No significant decay of the initial polarization state was observed within a measurement range of up to two days.

Mechanical force sensors using organic thin-film transistors

The pressure dependence of pentacene (C22H14) transistors with solution-processed polyvinylphenol gate dielectric on glass substrates is investigated by applying uniaxial mechanical pressure with a needle. We found that organic thin-film transistors are sensitive to applied pressure inherently. The measurements reveal a reversible current dependence of the transfer characteristics where the drain current is switching between two states. Experimental and simulation results suggest that switch-on voltage and interface resistance are affected. The change takes seconds, hinting at trap states being responsible for the effect.

Electrostrictive resonances in (Ba0.7Sr0.3)TiO3 thin filmsat microwave frequencies

The bias-voltage-dependent permittivity of (Ba0.7Sr0.3)TiO3(BST) thin films with thicknesses ranging from 100 to 250nm is investigated in the frequency range from 500MHz to 40GHz by impedance spectroscopy of integrated BST capacitors. The dielectric spectra of the films exhibit resonance phenomena in the 4–7GHz range when a bias field is applied. It is shown that the main controlling parameter of the resonance frequency is the film thickness. Calculations based on the strong electrostrictive activity of the BST films underline the assumption that the emission of plane acoustic waves is the underlying mechanism for this behavior.

Effect of anisotropic in-plane strains on phase states and dielectric properties of epitaxial ferroelectric thin films

A nonlinear thermodynamic theory is used to predict the equilibrium polarization states and dielectric properties of ferroelectric thin films grown on dissimilar substrates which induce anisotropic strains in the film plane. The “misfit strain-temperature” phase diagrams are constructed for single-domain PbTiO3 and Pb0.35Sr0.65TiO3 films on orthorhombic substrates. It is shown that the in-plane strain anisotropy may lead to the appearance of new phases which do not form in films grown on cubic substrates. The strain-induced dielectric anisotropy in the film plane is also calculated and compared with the anisotropy observed in Pb0.35Sr0.65TiO3 films deposited on NdGaO3.