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.

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 (<10 nm) and have a large bandgap (>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.

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.

The wake-up behavior of ferroelectric thin film capacitors based on doped hafnium oxide dielectrics in TiN-based metal-insulator-metal structures is reported. After field cycling a remanent polarization up to 40 C/cm 2 and a high coercive field of about 1MV/cm was observed. Doping of HfO2 by different dopants with a crystal radius ranging from 54pm (Si) to 132pm (Sr) was evaluated. In all cases, an improved polarization-voltage hysteresis after wake-up cycling is visible. For smaller dopant atoms like Si and Al stronger pinching of the polarization hysteresis appeared with increasing dopant concentration and proved to be stable during cycling. ©2014 The Japan Society of Applied Physics

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 report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4–20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization Pr of up to 10 μC cm−2 as well as a read/write endurance of 1.6 × 105 cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems

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