Seung Dam Hyun

Giant Negative Electrocaloric Effects of Hf0.5Zr0.5O2 Thin Films

Hafnia (HfO2 )-zirconia (ZrO2 ) solid solution films show giant positive (ΔT = 13.4 K) and negative (ΔT = -10.8 K) electrocaloric effects that can be simply controlled by tuning the Hf/Zr ratio. It is expected that the combination of the electrocaloric effects with opposite signs in this lead-free, simple, binary oxide can significantly improve the efficiency of electrocaloric cooling.

Study on the size effect in Hf0.5Zr0.5O2 films thinner than 8 nm before and after wake-up field cycling

The effects of film thickness and wake-up field cycling on the ferroelectricity in Hf0.5Zr0.5O2 films thinner than 8 nm were carefully examined. The Hf0.5Zr0.5O2 films became more antiferroelectric-like with decreasing film thickness in pristine state, whereas all the Hf0.5Zr0.5O2 films showed ferroelectric characteristics after wake-up process. The decrease in the coercive field with decreasing film thickness could be understood based on the depolarization correction. From the temperature-dependent characterization, the tetragonal-to-orthorhombic phase transition during wake-up process is believed to be a thermally activated process, and the estimated activation energy was ∼3.42 ± 0.17 kJ/mol.

Study on the internal field and conduction mechanism of atomic layer deposited ferroelectric Hf0.5Zr0.5O2 thin films

The internal field (Eint) in ferroelectric films is an important factor which can affect the reliability of practical devices utilizing two memory states which results from the remanent polarizations of ferroelectric films. In the current work, the Eint in TiN/Hf0.5Zr0.5O2/TiN capacitors was controlled by changing the annealing atmosphere (N2, O2, and forming gas). The magnitude of negative Eint in O2-annealed samples was the largest, whereas that in the forming gas-annealed sample was the smallest. The magnitude of Eint can be understood based on the asymmetric distribution of oxygen vacancies near top and bottom TiN electrodes. Despite the large magnitude of Eint, the two remanent polarizations can be reliably retained due to the large coercive electric field of Hf0.5Zr0.5O2 films, and this is expected to be beneficial for application in semiconductor memory devices. During the repetitive electric field cycling for the wake-up process, the change in Eint in O2- and forming gas-annealed samples showed the opposite tendency: the magnitude of Eint in the O2-annealed Hf0.5Zr0.5O2 film decreased, whereas that in the forming gas-annealed film increased. This difference is believed to be due to the redistribution of oxygen vacancies with electric field high enough for the migration of oxygen vacancies. The conduction mechanism of electrons through Hf0.5Zr0.5O2 films was also examined, and the results fitted best with the Poole–Frenkel emission model with the shallow traps for all the samples with a reasonable optical dielectric constant value for Hf0.5Zr0.5O2.

Ferroelectricity in undoped-HfO2 thin films induced by deposition temperature control during atomic layer deposition

HfO2 thin films, extensively studied as high-k gate dielectric layers in metal-oxide-semiconductor field effect transistors, have attracted interest of late due to their newly discovered ferroelectricity in doped HfO2. The appearance of the ferroelectric orthorhombic phase of HfO2 was previously examined in variously doped and undoped systems, but the effects of process-variable changes on the physical and chemical characteristics of a thin film and the resulting ferroelectricity have not been studied systematically. Here, the evolution of ferroelectricity in HfO2 thin films through deposition temperature control during atomic layer deposition was systematically examined without the intentional doping of metallic elements other than Hf. The lower-temperature-deposited HfO2 showed an increased impurity concentration, which was mainly carbon, and the involvement of these impurities suppressed the lateral grain growth during the crystallization thermal treatment. The grain size reduction could stabilize the metastable orthorhombic phase, whose surface and grain boundary energies are lower than those of the room-temperature-stable monoclinic phase, by increasing the grain boundary areas. The 9 nm-thick HfO2 thin film deposited at 220 °C exhibited a remanent polarization value of 10.4 μC cm−2 and endured up to 108 switching cycles, which is a 102-fold improvement compared to the previously reported undoped 6 nm-thick HfO2. This can be ascribed to the decrease in the relative portion of defective interfacial layers by increasing the total film thickness. The strategy of using deposition temperature control is a feasible method for the fabrication of these new lead-free binary ferroelectric thin films.

Time-Dependent Negative Capacitance Effects in Al2O3/BaTiO3 Bilayers

The negative capacitance (NC) effects in ferroelectric materials have emerged as the possible solution to low-power transistor devices and high-charge-density capacitors. Although the steep switching characteristic (subthreshold swing < sub-60 mV/dec) has been demonstrated in various devices combining the conventional transistors with ferroelectric gates, the actual applications of the NC effects are still some way off owing to the inherent hysteresis problem. This work reinterpreted the hysteretic properties of the NC effects within the time domain and demonstrated that capacitance (charge) boosting could be achieved without the hysteresis from the Al2O3/BaTiO3 bilayer capacitors through short-pulse charging. This work revealed that the hysteresis phenomenon in NC devices originated from the dielectric leakage of the dielectric layer. The suppression of charge injection via the dielectric leakage, which usually takes time, inhibits complete ferroelectric polarization switching during a short pulse time. It was demonstrated that a nonhysteretic NC effect can be achieved only within certain limited time and voltage ranges, but that these are sufficient for critical device applications.

Preparation and characterization of ferroelectric Hf0.5Zr0.5O2 thin films grown by reactive sputtering

HfO2-ZrO2 solid-solution films were prepared by radio frequency sputtering, and the subsequent annealing process was optimized to render enhanced ferroelectric behavior. The target power, working pressure and O2 partial pressure ratios were varied, along with the annealing gas, time and temperature. Then, the films structural and electrical properties were carefully scrutinized. Oxygen-deficient conditions were necessary during the sputter deposition to suppress grain growth, while annealing by O2 gas was critical to avoid defects and leakage problems. It is expected that the grain size difference under various deposition conditions combined with the degree of TiN top and bottom electrode oxidation by O2 gas will result in different ferroelectric behaviors. As a result, Hf0.5Zr0.5O2 prepared by radio frequency sputtering showed optimized ferroelectricity at 0% of O2 reactive gas, with a doubled remnant polarization value of ∼20 μC cm-2 at a thickness of 11 nm. Film growth conditions with a high growth rate (4-5 nm min-1) were favorable for achieving the ferroelectric phase film, which feasibly suppressed both the grain growth and accompanying monoclinic phase formation.

Interfacial charge-induced polarization switching in Al2O3/Pb(Zr,Ti)O3 bi-layer

Detailed polarization switching behavior of an Al2O3/Pb(Zr,Ti)O3 (AO/PZT) structure is examined by comparing the phenomenological thermodynamic model to the experimental polarization–voltage (P-V) results. Amorphous AO films with various thicknesses (2–10 nm) were deposited on the polycrystalline 150-nm-thick PZT film. The thermodynamic calculation showed that the transition from the ferroelectric-like state to the paraelectric-like state with increasing AO thickness occurs at ∼3 nm thickness. This paraelectric-like state should have exhibited a negative capacitance effect without permanent polarization switching if no other adverse effects are involved. However, experiments showed typical ferroelectric-like hysteresis loops where the coercive voltage increased with the increasing AO thickness, which could be explained by the carrier injection through the thin AO layer and trapping of the carriers at the AO/PZT interface. The fitting of the experimental P-V loops using the thermodynamic model considering the depolarization energy effect showed that trapped charge density was ∼±0.1 Cm−2 and critical electric field at the Pt electrode/AO interface, at which the carrier transport occurs, was ∼±10 MV/cm irrespective of the AO thickness. Energy band model at each electrostatic state along the P-V loop was provided to elucidate correlation between macroscopic polarization and internal charge state of the stacked films.

Research Update: Diode performance of the Pt/Al2O3/two-dimensional electron gas/SrTiO3 structure and its time-dependent resistance evolution

Time domain electric pulse measurements were conducted on a capacitor consisting of a Pt film as the top electrode, atomic-layer-deposited 6.5-nm-thick amorphous Al2O3 as the dielectric layer, and two-dimensional electron gas (2DEG) at the interface between Al2O3 and SrTiO3 as the bottom electrode. The sample showed highly useful current-voltage characteristics as the selector in cross-bar array resistance switching random access memory. The long-term (order of second) variation in the leakage current when the Pt electrode was positively biased was attributed to the field-induced migration of oxygen vacancies between the interior of the Al2O3 and the 2DEG region. Relaxation of the vacancy concentration occurred even at room temperature.

Voltage Drop in a Ferroelectric Single Layer Capacitor by Retarded Domain Nucleation

Ferroelectric (FE) capacitor is a critical electric component in microelectronic devices. Among many of its intriguing properties, the recent finding of voltage drop (V-drop) across the FE capacitor while the positive charges flow in is especially eye-catching. This finding was claimed to be direct evidence that the FE capacitor is in negative capacitance (NC) state, which must be useful for (infinitely) high capacitance and ultralow voltage operation of field-effect transistors. Nonetheless, the NC state corresponds to the maximum energy state of the FE material, so it has been widely accepted in the community that the material alleviates that state by forming ferroelectric domains. This work reports a similar V-drop effect from the 150 nm thick epitaxial BaTiO3 ferroelectric thin film, but the interpretation was completely disparate; the V-drop can be precisely simulated by the reverse domain nucleation and propagation of which charge effect cannot be fully compensated for by the supplied charge from the external charge source. The disappearance of the V-drop effect was also observed by repeated FE switching only up to 10 cycles, which can hardly be explained by the involvement of the NC effect. The retained reverse domain nuclei even after the subsequent poling can explain such behavior.