Metal-ferroelectric-metal Capacitors Research Articles

(Invited) Role of Oxidant Gas for Atomic Layer Deposition of HfxZr1−XO2 Thin Films on Ferroelectricity of Metal-Ferroelectric-Metal Capacitors

Since the first report of ferroelectricity in HfxZr1−xO2 (HZO) in 2011 [1], a lot of attention has been devoted for future non-volatile memory device applications due to its scalability (< 10 nm), low thermal budget (< 400°C) and matured atomic layer deposition (ALD) technique [2]. The thermal ALD process using H2O or O3 is generally employed for the fabrication of ferroelectric HZO thin films. On the other hand, the effect of the plasma-enhanced ALD process using O2 plasma gas on the crystallinity and ferroelectricity has not been systematically clarified. In this paper, we report the importance of ALD oxidant gases for HZO films using H2O or O2 plasma on the ferroelectricity of metal–ferroelectric–metal (MFM) capacitors.MFM capacitors with the H2O- and O2 plasma-based HZO films were fabricated as follows. A 10-nm-thick HZO films were deposited on a TiN bottom-electrode (BE-TiN) by ALD at 300°C using H2O or O2 plasma as oxidant gases and (Hf/Zr)[N(C2H5)CH3]4 (Hf:Zr = 1:1) cocktail precursor. The Hf/Zr ratios in both types of HZO films were estimated to be 0.4/0.6 using X-ray photoelectron spectroscopy (XPS). Next, a post-deposition annealing (PDA) process was carried out at 400 °C for 1 min under a N2 atmosphere. Finally, a TiN top-electrode was deposited by DC sputtering.First, the crystallinity and remanent polarization (2P r = P r + − P r −) of the H2O- and O2 plasma-based HZO films were investigated. Nanocrystals with ferroelectric orthorhombic (O), tetragonal (T), cubic (C) phases partially existed in the O2 plasma-based film after the ALD process, while an amorphous structure dominantly existed in the H2O-based film, analyzed by the grazing-incidence X-ray diffraction analysis and cross-sectional transmission electron microscopy images [3]. This could be because of a strong oxidation power and high energy ion/electron bombardment of O2 plasma. After the PDA process, the O phase was formed more in the O2 plasma-based HZO film than the H2O-based film. Therefore, the nanocrystal grains in the as-grown O2 plasma-based HZO film could play an important role as nuclei for the crystallization and formation of O phase [3,4]. From the polarization–electric field hysteresis curves, the PDA-treated O2 plasma-based capacitor exhibited 2P r of 20 µC/cm2, which was 1.5 times higher than that (13 µC/cm2) of the H2O-based capacitor. Thus, these results indicate that the crystallization and O phase formation of HZO films were promoted by using O2 plasma gas as an ALD oxidant, resulted in a higher 2P r.Next, endurance properties of these MFM capacitors were evaluated. In the wake-up state, both capacitors showed almost the same increase rate (~8%) of switching polarization (P sw). In the fatigued state, on the other hand, the O2 plasma-based capacitor exhibited less P sw degradation (~33%) after 106 cycles, whereas the P sw of H2O-based capacitor decreased by ~47%. To clarify these different fatigue properties, the TiOxNy interface reaction layer (IRL) formation at the HZO/BE-TiN interface was analyzed using synchrotron hard X-ray photoelectron spectroscopy (HAXPES). For the HAXPES Ti 2p spectra, the Ti-O peak intensity for the O2 plasma-based capacitor was larger than that of the H2O-based capacitor [5]. Therefore, an oxygen-rich TiON-IRL could be formed at the HZO/BE-TiN interface during ALD process due to the stronger oxidizing power of O2 plasma. Additional oxygen vacancies (VO) were reported to formed in HfO2-based films during field cycling due to the interface reaction between the HfO2-based film and TiN electrode. Moreover, one of the origins of the P sw degradation was thought to be domain pinning caused by VO [6]. Therefore, an oxygen-rich TiON-IRL for the MFM capacitor with the O2 plasma-based HZO film could prevent the interface reaction and formation of additional VO in HZO films, led to superior fatigue properties.In summary, the MFM capacitor with the O2 plasma-based HZO film showed superior 2Pr and fatigue resistance compared to those of the H2O-based one. Based on these experimental results, it is important to consider the selection of an ALD oxidant for fabrication of HZO-based MFM capacitors.This work was partly supported by JSPS KAKENHI (Nos. JP21J01667, JP20H02189, and JP18J22998) and MEXT Leading Initiative for Excellent Young Researchers (No. JPMXS0320220213). The HAXPES measurements were performed under approval of the NIMS Synchrotron X-ray Station (2020A4602 and 2020A4651).[1] J. Müller et al., Appl. Phys. Lett. 99, 112901 (2011).[2] J.-H. Kim et al., ACS Appl. Electron. Mater. 5, 4726 (2023).[3] T. Onaya et al., APL Mater. 10, 051110 (2022).[4] T. Onaya et al., Microelectron. Eng. 215, 111013 (2019).[5] T. Onaya et al., Solid State Electron. 210, 108801 (2023).[6] M. Pešić et al., Adv. Funct. Mater. 26, 4601 (2016).

(Invited) Polarization Stability Improvement for Hf0.5Zr0.5O2-Based Ferroelectric Capacitor

The instability in polarization during the endurance test of Hf0.5Zr0.5O2 (HZO) ferroelectrics thin films including the wake-up and the fatigue are still major challenges for the development of HZO-based ferroelectric memories. In this work, we will review the proposed mechanisms of the instabilities in polarization including wake-up and fatigue of the HZO-based metal-ferroelectric-metal (MFM) capacitors. Then, the material processing techniques to address the issues of instabilities are provided. The in-situ deposition of electrode and ferroelectric layers by atomic layer deposition (ALD) attracted considerable attention as a promising solution. Owing to the improved interface quality, both the endurance characteristics and remanent polarization were enhanced. We have also developed a HfO2/ZrO2 superlattice structure to further enhance the ferroelectric endurance of the MFM capacitors. The superlattice MFM capacitors show wake-up free characteristics with excellent endurance. The device performances and endurance characteristics of ferroelectric thin film transistor will also be presented.

(Invited) Role of Oxidant Gas for Atomic Layer Deposition of HfxZr1−XO2 Thin Films on Ferroelectricity of Metal-Ferroelectric-Metal Capacitors

We fabricated 400°C-annealed TiN/HfxZr1−xO2 (HZO)/TiN metal–ferroelectric–metal (MFM) capacitors using H2O and O2 plasma as oxidant gases of thermal (TH) and plasma-enhanced atomic layer deposition (PE-ALD), respectively, for HZO films. The PE-ALD film formed a more ferroelectric orthorhombic phase compared with the TH-ALD case. Therefore, the MFM capacitor with the PE-ALD film showed higher remanent polarization and dielectric constant. For the PE-ALD case, moreover, an oxygen-rich interfacial layer (O-rich-IL) was formed between the HZO film and TiN-bottom electrode during the ALD process. Thus, the MFM capacitor with the PE-ALD film showed less degradation of switching polarization during field cycling compared with the TH-ALD case, because an O-rich-IL should prevent the interface reaction and formation of additional oxygen vacancies in the PE-ALD film during field cycling. Based on these results, it is important to consider the selection of an ALD oxidant gas for the fabrication of HZO-based MFM capacitors.

Enhancement of remnant polarization in ferroelectric HfO2 thin films induced by mechanical uniaxial tensile strain after the crystallization process

The effect of strain on the ferroelectricity of HfO2 thin films after crystallization was investigated by applying uniaxial mechanical strains to Au/HfO2/TiN metal–ferroelectric–metal (MFM) capacitors. The remnant polarization (2P r) of MFM capacitors increased when tensile strain was applied during polarization switching. This phenomenon should not be attributed to phase transformation from the non-ferroelectric to the ferroelectric phase, taking account of the fast relaxation of 2P r after removal of the mechanical strain and the fact that the crystal structure of HfO2 thin films evaluated by grazing incidence X-ray diffraction measurement was not changed by the tensile strain.

Development of ferroelectricity with crystallographic phase transformation in Hf0.5Zr0.5O2 thin films upon initial stimulation of an electric field exceeding the coercive field

This study demonstrates a drastic transformation of ferroelectricity and crystallographic phase in Hf0.5Zr0.5O2 (HZO) thin films through the first stimulation of an electric field larger than the coercive field in metal-ferroelectric-metal (MFM) capacitors. Initially, capacitance–voltage (C–V) measurements in fresh MFM capacitors with voltage sweep smaller than the coercive field indicated constant capacitance value without hysteresis. Applying the electric field exceeding the coercive field subsequently, the C–V behavior changed to a typical dual-peak ferroelectric feature in positive and negative sweeps. X-ray diffraction analysis of the HZO layers before and after a single electric-field application revealed small-angle shifts in diffraction peaks, confirming a crystallographic phase transformation induced by the single electric-field stimulation exceeding the coercive field. These results suggest a possibility that the first electric field apply initiates development of ferroelectric phase transformation from a non-ferroelectric phase.

(Invited) Fabrication Technique of Ferroelectric HfxZr1−XO2 Thin Films Using ALD-ZrO2 Nucleation Layers

Ferroelectric HfxZr1−xO2 (HZO) thin films have attracted considerable attention towards high-density and low-power ferroelectric memory devices of ferroelectric random access memory (FeRAM) and ferroelectric field-effect transistors (FeFETs) [1]. To obtain ferroelectric orthorhombic (O) phase of HZO films, several techniques have been investigated, such as the TiN stressor layer technique [2] and controlled annealing conditions [3]. On the other hand, we pay attention to the ZrO2 nucleation layer technique because ZrO2 films deposited by atomic layer deposition (ALD) method formed a nanocrystalline structure and consisted dominantly of O, tetragonal (T), and cubic (C) phases, whose lattice constants are considerably close to that of ferroelectric O phase for HfO2 [4]. In this paper, we report the crystallinity and ferroelectricity of HZO films fabricated using the ZrO2 nucleation layer technique for metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors.First, four types of MFM capacitors of TiN/HZO/TiN (MFM w/o), TiN/HZO/bottom-ZrO2/TiN (MFM B-ZrO2), TiN/top-ZrO2/HZO/TiN (MFM T-ZrO2), and TiN/top-ZrO2/HZO/bottom-ZrO2/TiN (MFM D-ZrO2) were systematically investigated for the FeRAM applications [5]. The thicknesses of the ALD-grown HZO and ZrO2 films were 10 and 2 nm, respectively. The post-deposition annealing was performed at 600°C. The remanent polarization (2P r = P r + − P r −) of the MFM capacitors increased in the following order: MFM w/o (12 µC/cm2) < MFM B-ZrO2 (15 µC/cm2) < MFM T-ZrO2 (23 µC/cm2) < MFM D-ZrO2 (29 µC/cm2), while all capacitors showed almost the same coercive electric field (E c) value of around 1.2 MV/cm. Therefore, maximum 2P rvalue of the MFM capacitor was obtained using the top- and bottom-ZrO2 nucleation layers. For the MFM capacitors with ZrO2 nucleation layers, epitaxial-like grain growth of the HZO film occurred on the nanocrystalline top- and bottom-ZrO2 layers. Moreover, the relative ratio of O/T/C phases in the ferroelectric film, which was estimated using the peak area ratio of O(111)/T(101)/C(111)/{M(−111)+ O(111)/T(101)/C(111)+M(111)}, increased in the following order: MFM w/o < MFM B-ZrO2 < MFM T-ZrO2 < MFM D-ZrO2. Therefore, the top- and bottom-ZrO2 layers play an important role as nucleation layers for the crystallization of the HZO film, resulting in a larger relative ratio of O/T/C phases in the ferroelectric film compared to w/o. Moreover, these results indicate that the top-ZrO2 layer was more effective to form the ferroelectric phase compared to the bottom-ZrO2 layer.Next, two types of MFS capacitors of TiN/HZO/Si (MFS w/o) and TiN/top-ZrO2/HZO/Si (MFS T-ZrO2) were fabricated by low-temperature processes at 300°C of ALD and post-metallization annealing (PMA) for the FeFET applications [6]. The thicknesses of both HZO and ZrO2 films were 10 nm. Both MFS w/o and MFS T-ZrO2 were found to form an extremely thin SiO2 interfacial layer with a thickness of one or two monolayers between the HZO film and Si substrate due to a low temperature fabrication process of 300°C. The HZO film of the MFS T-ZrO2 formed O/T/C phases even with a low thermal budget of 300°C, while that of the MFS w/o had an amorphous structure. This result is attributed to the beneficial role of the nanocrystalline top-ZrO2 nucleation layer for the crystallization of an amorphous HZO film during the PMA process. Therefore, a higher 2P r value of 15 µC/cm2 was obtained for the MFS T-ZrO2 than that (2.2 µC/cm2) for the MFS w/o. Moreover, the endurance properties of the MFS T-ZrO2 were free from the wake-up effect and exhibited less degradation of switching polarization (P sw). This could be attributed to the insertion of a ZrO2 film at the TiN/HZO interface, which promoted the preferential formation of the ferroelectric orthorhombic phase and prevent the formation of oxygen vacancies at the ZrO2/HZO interface. Thus, we concluded that superior ferroelectricity with wake-up free properties and higher fatigue resistance of HZO-based MFS capacitors were achieved by using the ZrO2 nucleation layer technique.These results suggest that the fabrication technique of ferroelectric HZO films using nanocrystalline ALD-ZrO2 nucleation layers is one of the promising processes for the next-generation non-volatile memory device applications.This work was supported by JSPS KAKENHI (Nos. JP21J01667, JP20H02189, and JP18J22998) and MEXT Leading Initiative for Excellent Young Researchers (No. JPMXS0320220213).[1] T. Mikolajick et al., J. Appl. Phys. 129, 100901 (2021).[2] S. J. Kim, et al., Appl. Phys. Lett. 111, 242901 (2017).[3] S. Migita et al., Jpn. J. Appl. Phys. 58, SBBA07 (2019).[4] T. Onaya et. al., Appl. Phys. Express. 10, 081501 (2017).[5] T. Onaya et al., APL Mater. 7, 061107 (2019).[6] T. Onaya et al., APL Mater. 10, 051110 (2022).

In-Situ Reflectance Absorption Infra-Red Spectroscopy (RAIRS) Study on ALD of HfO2 on TiN and Pt Electrodes

Ferroelectricity in hafnia fluoride analogues has been widely investigated for nonvolatile memory applications. Although ALD of HfO2 technology is enough mature for CMOS technology, hafnia-based ferroelectrics still suffer from major reliability issues such as relaxation, imprint, fatigue, and breakdown.1 These reliability characteristics are thought to be related to the interface conditions between the ferroelectric film and the electrode. Thus, many reports suggested routes to enhance reliability and ferroelectric characteristics by modifying the interface states of the metal-ferroelectric-metal (MFM) capacitors. Unfortunately, only few reports disclose direct observation on evolution of interface formation and its mechanism. Recently, it is reported that scaling down the ferroelectric hafnia-based films to a few nm range dramatically improves the MFM capacitors’ reliability where the series capacitance and surface effect dominate, making it crucial to understand the interface properties carefully.2 In this presentation, we perform In-situ characterization using reflectance absorption infrared spectroscopy (RAIRS) to monitor the surface reaction and interface formation while HfOx ALD using TDMA-Hf with various oxidation reactants, such as H2O, O3, and anhydrous H2O2. TiN and Pt bottom electrodes are investigated at 250 °C. The RAIRS results show that the initial exposure of the oxidant generates the most amount of oxidation on the TiN surface by showing Ti-O and TiN-O peaks which were not observed for the Pt substrate. Moreover, the Ti-O and TiN-O peak area increase versus the dosing time of oxidant was minimum for H2O, and O3 showed continuous peak increase even after 12 s exposure. Interestingly, for the H2O2 case, there was almost no peak increase in the Ti-O bond region like H2O, but the TiN-O and TiO-O peaks appeared after the first 3 s and saturated after 6 s exposure. Also, not only on the TiN substrate, the peak for O-O stretching was observed for the Pt substrate as well, indicating that the H2O2 generates self-limiting peroxide bonds on the surface with a minimum interface formation. This suppressed interface formation with superior film properties using H2O2 might be the reason behind the robust reliability of the H2O2-based HZO capacitor. We are going to report reliability characteristics in conjunction with interface evolution.Acknowledements: We thank to YEST and KEIT for supporting the project through ISTD Program (No.20010806). This work is also supported by GRC-LMD program (task#3001.001) through SRC. The BRUTE hydrogen peroxide was provided by RASIRC. Ozone generator for TMEICReferences 1 J. Mohan et al., ACS AELM, 4, 4 (2022). 2 K. Toprasertpong et al., ACS AMI, 14 (2022).

Wake-up free ferroelectric hafnia-zirconia capacitors fabricated via vacuum-maintaining atomic layer deposition

Ferroelectric hafnium-zirconium oxide (HZO) is an excellent candidate for low-power non-volatile memory applications due to its demonstrated ferroelectricity at the nanoscale and compatibility with silicon-based technologies. The interface of HZO in contact with its electrode, typically TiN in a metal–ferroelectric–metal (MFM) capacitor configuration, is of particular interest because factors, such as volume confinement, impurity concentration, interfacial layers, thermal expansion mismatch, and defect trapping, are believed to play a crucial role in the ferroelectric performance of HZO-based devices. Processing variables, such as precursor type, oxygen source, dose duration, and deposition temperature, are known to strongly affect the quality of the oxide–metal interface. However, not many studies have focused on the effect of breaking or maintaining vacuum during MFM deposition. In this study, sequential, no-atmosphere processing (SNAP) is employed to avoid atmospheric exposure, where electrode TiN and ferroelectric HZO are deposited sequentially in the atomic layer deposition chamber without breaking vacuum. The effect of breaking vacuum during the sequential deposition steps is elucidated by fabricating and characterizing MFM capacitors with and without intentional vacuum breaks prior to the deposition of the HZO and top TiN. Using x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), we reveal that breaking vacuum after bottom TiN electrode deposition leads to interfacial oxidation and increased carbon contamination, which preferentially stabilizes the non-ferroelectric tetragonal phase and lead to diminished remanent polarization. Avoiding carbon impurities and interfacial TiOx at the HZO and TiN interface using SNAP leads to heightened remanent polarization, reduced leakage current density, and elimination of the wake-up effect. Our work highlights the effect of vacuum breaking on the processing-structure-properties of HZO-based capacitors, revealing that maintaining vacuum can significantly improve ferroelectric properties.

Design consideration of ferroelectric field-effect-transistors with metal–ferroelectric–metal capacitor for ternary content addressable memory

The performance of ferroelectric field-effect transistor (FeFET)-based ternary content addressable memory (TCAM) is examined to optimize the metal-ferroelectric-metal (MFM) capacitor of FeFET through a compact model based on the multi-domain Preisach theory. To reduce the search delay of the FeFET-based TCAM, the area of the MFM capacitor should be reduced, therefore enhancing polarization. Further, the effect of the polarization properties of ferroelectric material on the performance of the FeFET-based TCAM is explored. The increase in the polarization of ferroelectric material leads to better performance; however, the coercive voltage should also be optimized. As a result, to improve the performance of a circuit using FeFETs, simulations using reliable compact models are required. The results of this study can provide directions for developing ferroelectric materials.

Experimental study of endurance characteristics of Al-doped HfO2 ferroelectric capacitor

In this work, the endurance characteristics of Al-doped HfO2 (HAO)-based metal-ferroelectric-metal (MFM) capacitors (which were annealed at 1000 °C) with various doping concentrations were investigated. The doping concentration was optimized for the high annealing temperature (1000 °C) process. To investigate the impact of cycling pulses on the endurance characteristics of HAO-based MFM capacitor, the rise/fall time (t r/f ) and hold time (th ) for the cycling pulses were varied. Moreover, by adopting the recoverable fatigue process, the endurance characteristics under repetitive wake-up/fatigue processes were studied. The HAO capacitors achieved the remnant polarization (2Pr) of 23.767 μC cm−2 at pristine state under the high annealing temperature. Furthermore, it was demonstrated that the endurance characteristics (∼108 cycles) of the HAO capacitors were comparable to them of other HfO2-based ferroelectric capacitors. Lastly but not least, it turned out that the amount of oxygen and oxygen vacancies in the HAO thin film was dependent of doping concentrations for the film. The impact of oxygen and oxygen vacancies was quantitatively analyzed, in detail, with TEM, XPS and GIXRD analysis.

Low-Frequency Noise Characteristics in HfO2-Based Metal-Ferroelectric-Metal Capacitors.

The transport mechanism of HfO2-based metal-ferroelectric-metal (MFM) capacitors was investigated using low-frequency noise (LFN) measurements for the first time. The current-voltage measurement results revealed that the leakage behavior of the fabricated MFM capacitor was caused by the trap-related Poole-Frenkel transport mechanism, which was confirmed by the LFN measurements. The current noise power spectral densities (SI) obtained from the LFN measurements followed 1/f noise shapes and exhibited a constant electric field (E) × SI/I2 noise behavior. No polarization dependency was observed in the transport characteristics of the MFM capacitor owing to its structural symmetry.

Impact of Ferroelectric Layer Thickness on Reliability of Back‐End‐of‐Line‐Compatible Hafnium Zirconium Oxide Films

Due to its ferroelectricity, hafnium oxide has attracted a lot of attention for ferroelectric memory devices. Amongst different dopant elements, zirconium is found to be beneficial due to the relatively low crystallization temperature of hafnium‐zirconium‐oxide (HZO), thus it is back‐end‐of‐line (BEoL) compatible. The thickness of HZO has a significant impact on ferroelectric device reliability. High operation temperatures and high endurance are important criteria depending on the application. Herein, various HZO thicknesses (7, 8, and 10 nm) in MFM (metal‐ferroelectric‐metal) capacitors are investigated at varying operation temperatures (25 to 175 °C) at varying electric fields (±3 to ±5.4 MV cm−1) with respect to polarization, leakage current, endurance, and retention. 7 nm HZO showed promising results with an endurance of 107 cycles, with a low leakage current density, and almost no retention loss after 10 years. Extrapolated results at operation conditions (±2 MV cm−1 and 10 MHz) showed an endurance of 1010 cycles.

Electrical characteristics investigation of ferroelectric memories using stacked and mixed hafnium zirconium oxides

• Ferroelectric characteristics of mixed and stacked HfZrO devices were investigated. • Stacked HfZrO device showed a much stronger ferroelectricity than mixed one. • A surface nitrogen plasma treatment can alleviate ferroelectric domain pinning. • Nitrogen incorporation into stacked HfZrO further improved the endurance cycling. In this work, we investigate ferroelectric characteristics of hafnium zirconium oxide (HfZrO) metal-ferroelectric-metal (MFM) devices with mixed and stacked film structure. The experimental results reveal that the stacked HfZrO MFM device has a lower dynamic leakage and stronger ferroelectric polarization value of approximately 27.3 μC/cm 2 , which is much higher than 17.5 μC/cm 2 measured from mixed HfZrO MFM device. From endurance cycling test, we also confirm that the stacked HfZrO MFM capacitor with a remote nitrogen plasma treatment featuring a large initial hysteresis window can achieve a stable operation up to 10 8 cycles at an operating voltage of 2.5 V, which is even longer than that of mixed HfZrO MFM capacitor by one order of magnitude. Therefore, the stacked MFM structure with proper interface engineering provides a promising approach for the process integration of ferroelectric memory under the comprehensive consideration of device performance and endurance.

Improved Ferroelectric Properties in Hf0.5Zr0.5O2 Thin Films by Microwave Annealing.

In the doped hafnia(HfO2)-based films, crystallization annealing is indispensable in forming ferroelectric phases. In this paper, we investigate the annealing effects of TiN/Hf0.5Zr0.5O2/TiN metal-ferroelectric-metal (MFM) capacitors by comparing microwave annealing (MWA) and rapid thermal annealing (RTA) at the same wafer temperature of 500 °C. The twofold remanent polarization (2Pr) of the MWA device is 63 µC/cm2, surpassing that of the RTA device (40 µC/cm2). Furthermore, the wake-up effect is substantially inhibited in the MWA device. The orthorhombic crystalline phase is observed in the annealed HZO films in the MWA and RTA devices, with a reduced TiN and HZO interdiffusion in MWA devices. Moreover, the MFM capacitors subjected to MWA treatment exhibit a lower leakage current, indicating a decreased defect density. This investigation shows the potential of MWA for application in ferroelectric technology due to the improvement in remanent polarization, wake-up effect, and leakage current.

Characterization of Ferroelectric Characteristics for Hafnium Zirconium Oxide Capacitors with Refractory Electrodes

In this work, we investigated the ferroelectric properties of Hf0.5Zr0.5O2 (HZO) Metal-Ferroelectric-Metal (MFM) capacitors on various refractory electrodes, including TiN, TaN, W, and Mo. By comparing different electrodes and annealing temperature, we found that the MFM capacitors with TiN and W electrodes showed both higher remanent polarization (2Pr) and lower leakage current for post-metal annealing (PMA) temperatures ranging from 400 °C to 600 °C. Moreover, the MFM capacitor with W electrode showed better saturated polarization-voltage (P-V) curve and less “wake up effect” during the polarization switching cycles, while the MFM capacitor with TiN electrode showed the lowest leakage current. The correlation of crystallization quality studied by X-ray diffraction and the ferroelectric characteristics for each type of MFM capacitors were also presented and compared in this study.

Anomalous change of carrier transport property of ferroelectric Hf0.5Zr0.5O2 thin films in the first poling treatment

Carrier transport properties of ferroelectric Hf0.5Zr0.5O2 thin films have been investigated on a metal–ferroelectric–metal (MFM) capacitor in the first current flow of ferroelectric poling treatment. In the current–voltage (I–V) measurement of the MFM capacitor, a kink or discontinuity point of the derivative in the I–V characteristics appears, and after a cyclic voltage sweep this kink disappears. This phenomenon is different from the ferroelectric instabilities after application of several thousand or million voltage cycles reported as wake-up and fatigue. From the analysis using a Poole–Frenkel plot of the I–V characteristics, it is suggested that irreversible trap generation by electric field application occurs in poling treatment.

Temperature- and Frequency-Dependent Ferroelectric Characteristics of Metal-Ferroelectric-Metal Capacitors with Atomic-Layer-Deposited Undoped HfO2 Films.

In this study, we evaluated the temperature- and frequency-dependent ferroelectric characteristics of TiN/undoped HfO2/TiN metal-ferroelectric-metal (MFM) capacitors in which an undoped HfO2 film was deposited through atomic layer deposition (ALD). Successful ferroelectric characteristics were achieved after postdeposition annealing at 650 °C, which exhibited a remanent polarization of 8 μC/cm2 and a coercive electric field of 1.6 MV/cm at 25 °C (room temperature). The ferroelectric property was maintained at 200 °C and decreased as the temperature increased. The ferroelectric property was completely lost above 320 °C and fully recovered after cooling. The frequency dependency was evaluated by bias-dependent capacitance–voltage and s-parameter measurements, which indicated that the ferroelectric property was maintained up to several hundred MHz. This study reveals the ultimate limitations of the application of an undoped HfO2 MFM capacitor.

Ferroelectric Polarization Enhancement in Hafnium-Based Oxides Through Capping Layer Engineering

In this work, we investigate that the capping layer (CL) engineering of aluminum oxide (AlOx) on the dopant-free hafnium oxide (HfOx) and the hafnium zirconium oxide (HfZrOx) ferroelectric metal-ferroelectric-metal (MFM) capacitors. The AlOx CL featuring large bandgap and excellent thermal stability offers a stable interface favorable for ferroelectric phase transition. Therefore, the ferroelectric polarization and high-temperature leakage current of HfZrOx MFM capacitor can be largely improved due to the combination of zirconium doping and AlOx capping effect. From the analysis of interface thermodynamic stability and leakage current mechanism, the AlOx CL effectively alleviates interface defect traps between electrode and ferroelectric HfZrOx, which lowers high-temperature leakage current, reduces ferroelectric domains pinning, enhances ferroelectric polarization, and stabilizes the long-term endurance cycling.

Ferroelectric Properties of HZO Ferroelectric Capacitors with Various Capping Electrodes and Annealing Conditions

HZO has drawn a lot of attention because they are CMOS compatible and possess promising ferroelectric properties. It was reported that the ferroelectric properties of HZO have strong dependence on the selection of electrode materials [1]. It has been exhibited that HZO with W and Mo electrodes showed enhanced polarization [2]. On the other hand, TiN and TaN electrodes are highly interested in the CMOS compatible fabrication process. In this study, we fabricated ferroelectric HZO Metal-Ferroelectric-Metal (MFM) structures with the four electrode materials including TiN, W, Mo, TaN (i.e. MFM=TiN/HZO/TiN, W/HZO/W, Mo/HZO/Mo, TaN/HZO/TaN). We demonstrated the ferroelectric properties of these MFM structures at annealing temperature of 300 ℃ , 400 ℃ , 500 ℃ , and 600 ℃ . The orthorhombic phase of samples with different electrodes and annealing temperature were investigated by GIXRD. The trends in remanent polarization and the coercive field were compared by the P-E measurement. The DC leakage was also revealed and compared by the I-V test. Detailed microstructure analysis for the MFM capacitors were also conducted using SEM and AFM.

Ferroelectric Properties of HZO Ferroelectric Capacitors with Various Capping Electrodes and Annealing Conditions

In this study, the ferroelectric HfZrO2 (HZO) Metal-Ferroelectric-Metal (MFM) structures with the various metal electrodes including TiN, W, Mo, TaN (i.e. MFM=TiN/HZO/TiN, W/HZO/W, Mo/HZO/Mo, TaN/HZO/TaN) were fabricated. We have characterized the ferroelectric properties and microstructure of these MFM structures at various annealing temperature. The orthorhombic phase of samples with different electrodes and annealing temperature were investigated by grazing incidence x-ray diffraction (GIXRD). Microstructure analysis for the MFM capacitors were also conducted using TEM. The trends in remanent polarization and the coercive field of MFM capacitors with differed electrodes were compared by the polarization-voltage (P-V) measurements.