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 C/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

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.

Structural incommensurate modulation rule in hexagonal Ba(Ti1-xMx)O3-δ (M = Mn, Fe) multiferroics AIP Advances 2, 042129 (2012) Water assisted gate induced temporal surface charge distribution probed by electrostatic force microscopy J. Appl. Phys. 112, 084329 (2012) Influence of target composition and deposition temperature on the domain structure of BiFeO3 thin films AIP Advances 2, 042104 (2012) Nanodomain structures formation during polarization reversal in uniform electric field in strontium barium niobate single crystals J. Appl. Phys. 112, 064117 (2012) The effect of the top electrode interface on the hysteretic behavior of epitaxial ferroelectric Pb(Zr,Ti)O3 thin films with bottom SrRuO3 electrode J. Appl. Phys. 112, 064116 (2012) Additional information on J. Appl. Phys. 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% YO 1.5 in HfO 2 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% YO 1.5 admixture the remanent polarization peaked at 24 lC=cm 2 with a coercive field of about 1.2 MV=cm. Considering the availability of conformal deposition processes and CMOS-compatibility, ferroelectric Y:HfO 2 implies high scaling potential for future, ferroelectric memories.

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.

We investigated phase transitions in ferroelectric silicon doped hafnium oxide (FE-Si:HfO2) by temperature dependent polarization and x-ray diffraction measurements. If heated under mechanical confinement, the orthorhombic ferroelectric phase reversibly transforms into a phase with antiferroelectric behavior. Without confinement, a transformation into a monoclinic/tetragonal phase mixture is observed during cooling. These results suggest the existence of a common higher symmetry parent phase to the orthorhombic and monoclinic phases, while transformation between these phases appears to be inhibited by an energy barrier