Effect of Y2O3 interlayer on the electric properties of Y-doped HfO2 film deposited by chemical solution deposition

Ferroelectric oxide becomes the focus of memory industry again after the discovery of ferroelectricity in doped-HfO₂ polycrystalline films. Thermal stress is an important factor for the variation of ferroelectric phase content. In this paper, the effect of film stress induced by Y₂O₃ interlayer in the ferroelectric properties of Y-doped HfO₂ (Y: HfO₂) ferroelectric films, which is deposited by chemical solution deposition (CSD), is investigated systematically by polarization-voltage measurement. Compared with Y-doped HfO₂ film without interlayer, 1 nm Y₂O₃ interlayer enhances the remanent polarization of Y: HfO₂ film due to the effects of film stress and surface energy. And thick Y₂O₃ interlayer benefits to reduce leakage current density. But polarization switching of HfO₂ film is restrained due to the capacitor voltage divider caused by thick Y₂O₃ interlayer. The obvious enhance effect of Y₂O₃ interlayer still exists in Y: HfO₂ film at high voltage due to the breakdown of Y₂O₃ interlayer, realizing a huge remanent polarization (P_r) of 22.8 μC/cm² in Y: HfO₂ film (doping content: 4 at %). It is 3.6 times than that of ferroelectric doped-HfO₂ film without Y₂O₃ interlayer.     

Modulation of ferroelectricity and antiferroelectricity of nanoscale ZrO2 thin films using ultrathin interfacial layers

In this study, tailoring the microstructures and ferroelectric(FE)/antiferroelectric(AFE) properties of nanoscale ZrO₂ thin films is demonstrated with an intentional introduction of sub-nanometre interfacial layers. The ferroelectricity of ZrO₂ thin films is significantly enhanced by the HfO₂ interfacial layers, while the TiO₂ interfacial layers lead to a dramatic transformation of ZrO₂ from ferroelectricity into antiferroelectricity. The HfO₂ and TiO₂ interfacial layers boost the formation of the polar orthorhombic phase with (111)-texture and the non-polar tetragonal phase with (110)-texture in the FE/AFE ZrO₂ thin films, respectively, as evidenced by grazing incidence, out-of-plane, and in-plane X-ray diffraction measurements. Furthermore, the modulation of ferroelectricity and antiferroelectricity of nanoscale ZrO₂ thin films by the HfO₂/TiO₂ interfacial layers can be achieved without high-temperature annealing, which is highly advantageous to process integration. The findings demonstrate the important role of the interfaces in the effective tuning of FE/AFE properties of nanoscale thin films.     

Ferroelectric ZrO2 ultrathin films on silicon for metal-ferroelectric-semiconductor capacitors and transistors

Enhanced ferroelectric properties of nanoscale ZrO₂ thin films by an HfO₂ seed layer are demonstrated in metal-ferroelectric-semiconductor (Si) capacitors and transistors prepared with a low thermal budget of 400 °C. The seeding effect of the HfO₂ layer leads to the enhancement of crystallization into the orthorhombic phase and the increase of remnant polarization of the sub-10 nm ZrO₂/HfO₂ bilayer structure. The ferroelectric field-effect transistor with the ZrO₂/HfO₂ bilayer gate stack reveals a large memory window of ~1.2 V and a steep subthreshold swing below 60 mV/decade. As compared with the Hf_0.5Zr_0.5O₂ thin film, superior ferroelectric properties of the ZrO₂/HfO₂ bilayer structure show great potential for ferroelectric memory devices fabricated on Si substrates.     

Ferroelectric yttrium doped hafnium oxide films from all-inorganic aqueous precursor solution

We report a unique aqueous solution deposition method to prepare yttrium doped hafnium oxide (Y:HfO₂) thin films using all-inorganic reagents. The composition and chemical bonding features of the films were investigated using X-ray photoelectron spectroscopy. The Y:HfO₂ film was integrated into metal-insulator-semiconductor (MIS) structure capacitors for electrical measurements. A transition of the polarization behavior from apparent ferroelectric-type to linear dielectric-type was observed for films with thickness increasing from 25?nm to 80?nm, which is correlated to the dominant crystal structure change from high-symmetry phase to monoclinic phase evidenced by grazing incidence X-ray diffraction analysis.     

Ferroelectric enhancement of Al-doped HfO2 thin films by rapid electron beam annealing in a low thermal budget

In past few years, there was a great amount of research on ferroelectric Al-doped HfO₂ (HAO) thin films which suffer from the need of high annealing temperatures to achieve significant ferroelectricity. In this work, we realize pronounced remnant polarization 2P_r~29μC/cm² of HAO using rapid electron beam annealing (EBA) with a large area. The simulation of electron beam trajectories reveals that the effect of EBA concentrates on the region ~20 nm below the sample surface, which highly benefits the process integration where a low thermal budget is required. The energy-dispersive X-ray and high-angle annular dark-field analyses reveal the interdiffusion between Al and Hf in the HAO layer treated by EBA. The pronounced ferroelectricity of HAO can be accounted for by the lattice strain, which facilities the formation of the orthorhombic phase, due to the substitution of Al for Hf as supported by the fast Fourier transformation diffraction pattern.     

Effect of annealing protection atmosphere on the ferroelectric yttrium doped hafnium oxide thin films

The 10 nm thick yttrium doped hafnium oxide (Y:HfO₂) thin films, prepared by chemical solution deposition which using all-inorganic aqueous salt reagents, were fabricated on Si (100) substrates. The crystalline structure, chemical composition and ferroelectric properties of thin films, annealed in protection atmosphere of Air, Ar and N₂, were examined. Result showed that the crystalline structure and ferroelectric properties of films exhibited a strong annealing protection atmosphere dependence. When compared to annealing protection atmosphere of Air and Ar, the films with the N₂ exhibited lowest m-phase fraction of 19.4%, and the highest oxygen vacancy percentage content of 3.06%, accompanied with the highest relative permittivity of 50.9 and the remanent polarization of 14.6 μC/cm². These excellent ferroelectric properties were correlated with asymmetric orthorhombic phase and the concentration of oxygen vacancy introduced from the nitrogen doping concentration.     

Multiferroic properties of La/Er/Mn/Co multi-doped BiFeO3 thin films

Bi_0.9-xLa_xEr_0.1Fe_0.96Co_0.02Mn_0.02O₃ (BLa_xEFMCO) thin films were prepared by sol-gel method. The grain size, grain boundary resistance, oxygen vacancies and the amount of Fe²⁺ of the films were reduced by multi-ion doping to reduce the built-in electric field of the films. An applied voltage was adopted to regulate the effects of the directional alignment of the oxygen vacancies, defects, and defect pairs on the ferroelectric domains at the grain boundaries to control the ferroelectric polarization of the films. Meanwhile, the capacitance peak also reveals the effects of the ferroelectric domains switching, the migration of oxygen vacancies, and the directional alignment of defect pairs on the ferroelectric properties. In addition, the remnant polarization value of the BLa_0.01EFMCO thin film reaches 152?μC/cm², the squareness of the hysteresis loop (R_sq) is calculated to be 1.03, and the maximum switching current is 1.50?mA. The typical butterfly curves under positive and negative electric fields indicate the films with the enhanced ferroelectric properties. Moreover, the BLa_0.01EFMCO thin film exhibits the enhanced ferromagnetic properties, and its saturation magnetization (M_s) is 2.32 emu/cm³. Therefore, the ferroelectric properties of the BFO film can be enhanced by the multi-ion doped BFO film to reduce the grain boundary resistance (Rgb), the interface Schottky barrier formed by the asymmetric electrode material at the top and bottom of the film, and the built-in electric field formed by the film internal defect or defect pairs.     

Chemical and interfacial design in the visible-light-absorbing ferroelectric thin films

Ferroelectric thin films with switchable polarization and anomalous photoelectric effects have received extensive attention recently. However, the improvement of photoelectric performance is accompanied by the weakening of ferroelectricity. Here, both chemical and interlayer design are used to regulate the polarization and optical properties of BiFeO₃-based ferroelectric films. We achieved an improvement in both ferroelectricity and bandgap by chemical composition. The remanent polarization has been enhanced to 73.8 μC/cm² from 0.2 μC/cm², ascribed to the structural transition. The band gap of Eu-BiFeO₃ films has been reduced to 2.23 eV from 2.42 eV due to the unique energy level from Eu 4f, indicating the enhanced visible-light-absorbing capability. We have designed a "sandwich" interfacial structure of homogeneous Eu-BiFeO₃ films. A clever combination between optimal ferroelectricity and narrow band gap with near Eu contents of BFO films would generate an interfacial layer with a homogeneous gradient component, which should favor the switching of ferroelectric domains. The results show that the remanent polarization improved by 17 % to 86.2 μC/cm² while the band gap has also improved. Intriguingly, the short-circuit current density (J_sc) and open circuit (V_oc) of the photovoltaic signal of the optimal films are 89.0 nA and 0.412 V, respectively. This provides a simple and intelligent way to design the ferroelectric-photoelectric thin films and lays the foundation for optical information storage devices.     

Sol-gel derived low temperature HfO2-GPTMS hybrid gate dielectric for a-IGZO thin-film transistors (TFTs)

In this study, we prepared inorganic-organic HfO₂-GPTMS hybrid films by a simple sol-gel method at low temperature for high-k dielectric gate applications. The hybrid films were deposited by spin coating process, followed by annealing at 150?°C. The hybrid dielectric material was characterized by Spectroscopic ellipsometry (SE), AFM, FESEM, FTIR, TGA, and XPS techniques. The resulting hybrid films exhibit homogeneous and smooth surface with high optical transparency. Their dielectric properties were analysed by measuring leakage current and capacitance versus voltage of metal-insulator-metal (MIM) capacitor structures. From this analysis, the leakage current density at ??5?V, capacitance and dielectric constant at 1?MHz measured on the hybrid films were 10^?7 A/cm², 51.3?nF/cm² and of 11.4 respectively. Finally, to investigate the electrical performance of the hybrid thin films as a dielectric gate in thin film transistors (TFTs), bottom-gate TFTs were fabricated by depositing the HfO₂-GPTMS dielectric gate layer on ITO-coated glass substrate and subsequently a sputtered a-IGZO thin film as the channel layer. The electrical response of the resulting TFTs demonstrated good saturation mobility of 4.74?cm² V^?1 s^?1, very low threshold voltage of 0.3?V and I_on/I_off current ratio of 10⁴, with low operating voltage under 8?V.     

Structural,Electrical, and Ferroelectric Properties of Nb‐Doped Na0.5Bi4.5Ti4O15 Thin Films

Ferroelectric Na_0.5Bi_4.5Ti₄O₁₅ (NaBTi) and donor Nb‐doped Na_0.5Bi_4.5Ti_3.94Nb_0.06O₁₅ (NaBTiNb) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates using a chemical solution deposition method. The doping with Nb⁵⁺‐ions leads to tremendous improvements in the ferroelectric properties of the NaBTiNb thin film. Room‐temperature ferroelectricity with a large remnant polarization (2P_r) of 64.1 μC/cm² and a low coercive field (2E_c) of 165 kV/cm at an applied electric field of 475 kV/cm was observed for the NaBTiNb thin film. The polarization fatigue study revealed that the NaBTiNb thin film exhibited good fatigue endurance compared with the NaBTi thin film. Furthermore, the NaBTiNb thin film showed a low leakage current density, which was 1.48 × 10^?6 A/cm² at an applied electric field of 100 kV/cm.     

Induction of ferroelectricity in nanoscale ZrO2 thin films on Pt electrode without post-annealing

Large stable ferroelectricity in nanoscale undoped zirconia (ZrO₂) thin films prepared without post-annealing has been demonstrated for the first time. Remanent polarizations up to 12 μC cm⁻² were obtained in the as-deposited ZrO₂ thin films prepared by remote plasma atomic layer deposition at 300 °C substrate temperature on the Pt electrode. Ferroelectric crystallization of the films was achieved without post-annealing, which is highly beneficial to the application of the films in non-volatile memories and ultralow-power nanoelectronics. The existence of the ferroelectric orthorhombic phase with noncentrosymmetric space group Pbc2₁ in the as-deposited ZrO₂ thin films was confirmed by high-resolution transmission electron microscopy.     

Effects of annealing temperature on structure and electrical properties of sol–gel derived 0.65PMN-0.35PT thin film

0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (0.65PMN-0.35PT) thin films were deposited on Pt/Ti/SiO₂/Si substrates annealed from 550 to 700 °C using sol-gel process. The effects of annealing temperature on microstructure, insulating, ferroelectric and dielectric properties were characterized. The result reveals that 0.65PMN-0.35PT thin films possess a polycrystalline structure, matching well with the perovskite phase despite the existence of a slight pyrochlore phase. The film samples annealed at all temperatures exhibit relatively dense surfaces without any large voids and the grain size increases generally with the increase of the annealing temperature. Meanwhile, pyrochlore phase is considerably generated because of the deformation of perovskite phase caused by volatilization of Pb at an excessive high-temperature. The film annealed at 650 °C exhibits superior ferroelectricity with a remanent polarization (P_r) value of 13.31 μC/cm², dielectric constant (ε_r) of 1692 and relatively low dielectric loss (tanδ) of 0.122 at 10⁴ Hz due to the relatively homogeneous large grain size of 130 nm and low leakage current of approximately 10^-6 A/cm².     

Focus on the ferroelectric polarization behavior of four-layered Aurivillius multiferroic thin film

The well-saturated ferroelectric hysteresis loops with double remnant polarization up to 50?μC/cm² were obtained in four layered Aurivillius-type multiferroic Bi₅FeTi₃O₁₅ thin film. Pulsed positive-up negative-down polarization measurements demonstrate the intrinsic ferroelectric polarization, which present optimal rectangularity and polarization value. The hysteresis loops measurements with larger frequency range of 0.2–100?kHz indicate stable and ultra-fast switching speed of ferroelectric domains. Persistent retention properties were observed, and they are also independent of the applied electric field. In fatigue test an increased dielectric constant is observed along with the suppression of switchable polarization. Both of them can be restored partly to their original values via the stimulating of high electric field. The block domain switching due to the oxygen vacancies aggregated on domain walls are discussed for those characteristics. It is providing important contributions of domain wall pinning in the polarization degradation of Aurivillius-type ferroelectric films with four layers.     

Ferroelectric properties of pure ZrO2 thin films by chemical solution deposition

Ferroelectricity in pure zirconia (ZrO₂) thin films, manufactured on Si (100) substrates via the chemical solution deposition method using all-inorganic aqueous salt precursor, has been demonstrated for the first time. The influence of thickness on the crystalline structure and ferroelectric properties of the thin films were measured and showed that they were strongly affected by the film thickness. The structural data indicated that as the film thickness increased from 30 nm to 50 nm, the m-phase fraction increased, and a phase transition from orthorhombic to cubic and then tetragonal occurred near the main diffraction peak of 30.7°. The lowest m-phase fraction of 15.4% was obtained in the pure ZrO₂ film with a thickness of 30 nm, and after 10³ field cycling, it exhibited the highest relative permittivity of 39.6 as well as the highest residual polarization of 8.5 μC/cm².     

Structural phase transition,electrical and photoluminescent properties of Pr3+-doped (1-x)Na0.5Bi0.5TiO3-xSrTiO3 lead-free ferroelectric thin films

Lead-free ferroelectric Pr³⁺-doped (1-x)Na_0.5Bi_0.5TiO₃-xSrTiO₃ (x?=?0–0.5) (hereafter abbreviated as Pr-NBT-xSTO) thin films were prepared on Pt/Ti/SiO₂/Si and fused silica substrates by a chemical solution deposition method combined with a rapid thermal annealing process at 700?°C, and their structural phase transition, dielectric, ferroelectric, and photoluminescent properties were investigated as a function of STO content. Raman analysis shows that with increasing STO content, the phase structures evolve from rhombohedral phase to coexistence of rhombohedral and tetragonal phases (i.e. morphotropic phase boundary), and then to tetragonal phase. The structural phase transition behavior has been well confirmed by temperature- and frequency- dependent dielectric measurements. Meanwhile, the variation in photoluminescence intensity of Pr³⁺ ions with different STO content in the NBT-xSTO thin films also indicates that there exists a clear structural phase transition when the film composition is close to the morphotropic phase boundary. Superior dielectric and ferroelectric properties are obtained in the Pr-NBT-0.24STO thin films due to the formation of morphotropic phase boundary. Our study suggests that Pr-NBT-xSTO thin films be promising multifunctional materials for optoelectronic device applications.     

Dielectric relaxation and resistive switching of Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4 thin films with different thicknesses of the Bi0.96Sr0.04Fe0.98Co0.02O3 layer

Bi_0.96Sr_0.04Fe_0.98Co_0.02O₃/CoFe₂O₄(BSFCO/CFO) bilayered thin films with different thicknesses of the BSFCO layer are synthesized on FTO/glass substrates by chemical solution deposition method (CSD). The influence of BSFCO thickness on the microstructure, dielectric relaxation, ferroelectric properties and resistive switching (RS) of the thin films are researched. Strain exists in the prepared thin films and gives rise to structural distortion, which has an effect on charged defects and ferroelectric polarization. Dielectric relaxation that is closely related to the interfacial polarization at the BSFCO/CFO interface is observed, and the dielectric loss peaks along with decreasing intensity shift to high frequency with decreasing strain. The Maxwell-Wagner two-layer model is adopted to investigate the mechanism of dielectric relaxation, and the relaxation time τ is calculated and it shown to be directly proportional to the strain. It is found that the dielectric properties, including low dielectric loss, can be improved by controlling the BSFCO layer thickness. The ferroelectric properties improve with the decreasing strain, the 12-BSFCO/CFO thin film possesses a large P_r ~ 102.9?μC/cm² at 660?kV/cm. The observed resistive switching (RS) behavior is attributed to the interfacial conduction mechanism, it is found that strain-dependent the ferroelectric polarization switching modulates the width of depletion layer and the height of potential barrier at the interface, resulting in the different resistance states.     

Variation in ferroelectric polarization direction of epitaxial (001) SrBi2Ta2O9 thin film induced by oxygen vacancy

We report the enhancement of c-axis ferroelectric properties in an epitaxial (001) SrBi₂Ta₂O₉ (SBT) thin film originating from the oxygen vacancy. We controlled the oxygen vacancy in the SBT thin film by using the electrical stress process triggering the polarization fatigue. As a result of the fatigue test for the Pt/SBT/Nb:STO capacitor, we observed the gradual increase in the ferroelectric polarization up to 10¹² fatigue cycles and then subsequently rapid decrease over 10¹² cycles. Based on piezoresponse force microscopy (PFM) measurements, we demonstrated the increase in the polarization and PFM signal resulting from the creation of oxygen vacancy.     

Ink-jet printed BNT thin films with improved ferroelectric properties via annealing in wet air

In this work, an ink-jet printing process based on the sol-gel route was applied to prepare lead-free ferroelectric Na_0.5Bi_0.5TiO₃(BNT) thin films for the first time. Dense and crack-free films with perovskite structure were obtained from a modified precursor solution through multiple printing and pyrolysis processes. The ferroelectric, dielectric and electrical properties were significantly affected by the annealing temperature and atmosphere. The film annealed at 670?°C in wet air showed a high remnant polarization of 24.7?μC/cm² with a low coercive field of 263?kV/cm, the dielectric constant and loss were 185 and 0.1 at 10?kHz, respectively. It was found that wet air was an alternative to reduce oxygen vacancies and enhance properties of ferroelectric films, which can be explained by the defect chemical reaction between water and oxygen vacancies. X-ray photoelectron spectroscopy(XPS) confirmed the decrease of oxygen vacancies after annealing with water presence, with a formation of Ohmic conduction mechanism dominated by charged hydroxyl groups.     

Polarization behavior of` lead-free 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 thin films with enhanced ferroelectric properties

(Bi_0.5Na_0.5)TiO₃ based ferroelectric lead-free thin films have great potential for modern micro-devices. However, the multicomponent feature and volatile nature of Bi/Na makes the achievement of high quality films challenging. In this work, the morphotropic phase boundary composition, 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ thin films were successfully prepared by CSD method. Dense films with low dielectric loss and low leakage current density were obtained. A well-defined polarization hysteresis loop with a high remnant polarization was observed in the thin films. Moreover, the polarization behavior of the film at original state, under electric field and upon heating was investigated by PFM. A self-polarization and asymmetric domain switching behavior were observed. High temperature induced depolarization and the self-polarization recovered upon cooling. The thin films with good quality show a promising potential for the application in electrical devices, and the in-depth investigation of the polarization behavior improves the understanding of ferroelectric and piezoelectric properties of thin films.     

Mixed grains and orientation-dependent piezoelectricity of polycrystalline Nd-substituted Bi4Ti3O12 thin films

Polycrystalline Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were prepared on Pt/Ta/glass substrates by a pulsed laser deposition method. X-ray diffraction measurements revealed that the BNT thin films were preferentially oriented along the (117) direction although they possessed a polycrystalline structure. Good ferroelectric properties of the BNT thin film were observed with a remnant polarization of 13 μC/cm² (2 P_r ~26 μC/cm²). The fatigue resistance test exhibited that the ferroelectric polarization of the BNT thin film degraded significantly after around 10⁹ switching cycles, which can be attributed to its crystal structure. We investigated the surface morphology and ferroelectric domain structure by atomic force microscopy (AFM) and piezoresponse force microscopy (PFM), respectively. Interestingly, mixed grains consisting of long and circular shapes were observed on the BNT film surface, which corresponded to a- and c-axes orientations of crystal growth, respectively. The PFM study revealed that the piezoelectric coefficient (d₃₃) of the long grains was much larger than that of the circular grains.