Artificially induced ferroelectric-like behavior in an antiferroelectric sandwich structure by interface engineering

Interface engineering is essential for achieving fascinating interfacial functionalities in a single all-oxide-interface-based device. In the present work, a sandwich structure (Pb_0.94La_0.06(Zr_0.95Ti_0.05)O₃ (PLZT)/HfO₂/ Pb_0.94La_0.06(Zr_0.95Ti_0.05)O₃) was fabricated via a chemical solution approach. A distinct “ferroelectricity-like” behavior with high P_max (～ 80 μC/cm²) and P_r (～ 36 μC/cm²) is demonstrated. The dielectric HfO₂ thin layer presents a tetragonal symmetry structure, which stabilizes a slight distorted structure of the upper PLZT layer (PLZT(T)) with a= 4.19(9) Å, b= 4.10(6) Å, β ～ 91.04?. In PLZT(T), the ferroelectric (FE) phase is identified as the matrix embedded with a small amount of AFE nanodomains, while the bottom PLZT layer (PLZT(B)) exhibits typical AFE incommensurately modulated structures. The near-interface structures in both PLZT layers are characterized by ferroelectric polarizations with head-to-tail configuration across the heterointerface. Such discontinuous, downward polarizations support the accumulation of oxygen vacancies at the heterointerface that facilitate the local polarization enhancement. It is the combination effect of stable ferroelectric polarization in the PLZT(T) layer, interfacial oxygen vacancies and large surface to volume ratio that leads to the superior polarization performance of the antiferroelectric sandwich structure. It indicates that interface engineering is a feasible approach to manipulate the ferroic behavior.     

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.     

Microstructure and ferroelectric properties of Ta-doped Bi3.25La0.75Ti3O12/ZnO thin film capacitors

Ta-doped Bi_3.25La_0.75Ti₃O₁₂(BLTT)/ZnO films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by a magnetron sputtering method. Firstly, ZnO crystal thin films were grown on the substrates by a reactive sputtering method. Then, BLTT thin films were deposited on the ZnO layers at room temperature and post-annealed at 600 °C. The micromorphology, ferroelectric and dielectric properties of BLTT/ZnO films were analyzed. The XRD analysis shows that ZnO buffer layer significantly reduces the crystallization temperature of BLTT thin film. The TEM results show that lamellar BLTT grains are grown on ZnO layer at a certain angle with few elements diffusion at the interface of ZnO phase and Bi₄Ti₃O₁₂ phase. The ferroelectric properties indicate that BLTT/ZnO films exhibit different remanent polarization and coercive fields under electric field with different directions. The novel mechanism of tailoring ferroelectric properties may open new possibilities for designing special ferroelectric devices.     

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 properties of ZrO2 films deposited on ITO-coated glass

In this work, the ferroelectric characteristics of ZrO₂ thin films grown on ITO-coated glass have been investigated. The ferroelectric nature of the ZrO₂ films has been studied by polarization-electric field (P-E) hysteresis loops and found to be optimum for the films processed by rapid thermal annealing at 600 °C. The increase in the annealing temperature improves the ferroelectric properties through the increase of the in-plane strain that causes the formation of the ferroelectric orthorhombic phase. The formation of the orthorhombic phase was confirmed through high-resolution transmission electron microscopy. The effect of the electric field on the polarization switching kinetics of ZrO₂ films has been investigated revealing that the switching kinetics follows the nucleation limited switching (NLS) model. The activation fields estimated from the peak values of the polarization currents (i_m) and the time (t_m) at which i_m occurs are in good agreement with the values obtained from the switching characteristic time of the NLS model. This work paves the way towards the integration of (pseudo)-binary oxide thin films on cheap substrates like glass for the next-generation of non-volatile memories.     

Bipolar resistive switching behavior and conduction mechanisms of composite nanostructured TiO2/ZrO2 thin film

In this work, TiO₂/ZrO₂ bilayer thin film was prepared on fluorine doped tin oxide (FTO)/glass substrates by using a simple and low-cost chemical solution deposition method. Reproducible bipolar resistive switching (RS) characteristics in Au/TiO₂/ZrO₂/FTO/glass devices are reported in this work. TiO₂/ZrO₂ bilayer thin films prepared in this work shows reversible bipolar resistive switching and unidirectional conduction performances under applying voltage and these special performances of TiO₂/ZrO₂ bilayer thin films was first reported. Obvious resistive switching performance can be observed after setting a compliance current, the ratio of high/low resistance reached about 100 at a read voltage of +0.1V and −0.1V and the RS properties showed no obvious degradation after 100 successive cycles tests. The resistive switching characteristics of Au/TiO₂/ZrO₂/FTO/glass device can be explained by electron trapping/detrapping related with the vacancy oxygen defects in TiO₂/ZrO₂ bilayer thin film layer. According to slope fitting, the main conduction mechanisms of the sample are Ohmic and Space charge limited current mechanism.     

Structural and electrical properties of Na0.5Bi4.0RE0.5Ti4O15 (RE=Tm,Yb and Lu) thin films

In the current study, a series of lanthanide ions, Tm, Yb and Lu, were used for doping at the Bi-site of the Aurivillius phase Na_0.5Bi_4.5Ti₄O₁₅ (NaBTi) to investigate the structural, electrical and ferroelectric properties of the thin films. In this regard, Na_0.5Bi_4.5Ti₄O₁₅ and the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5i₄O₁₅ (RE=Tm, Yb and Lu, denoted by NaBTmTi, NaBYbTi, and NaBLuTi, respectively) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Formations of the Aurivillius phase orthorhombic structures for all the thin films were confirmed by X-ray diffraction and Raman spectroscopic studies. Based on the experimental results, the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5Ti₄O₁₅ thin films exhibited a low leakage current and the improved ferroelectric properties. Among the thin films, the NaBLuTi thin film exhibited a low leakage current density of 6.96×10⁻⁷ A/cm² at an applied electric field of 100 kV/cm and a large remnant polarization (2P_r) of 26.7 μC/cm² at an applied electric field of 475 kV/cm.     

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.     

Magnetoelectric coupling effect of Ga0.8Fe1.2O3/Bi0.5(Na0.85K0.15)0.5TiO3 multiferroic composite films

Lead-free Ga_0.8Fe_1.2O₃/Bi_0.5(K_0.15Na_0.85)_0.5TiO₃ (GFO/BKNT) bilayer multiferroic composite films were fabricated on Pt(100)/Ti/SiO₂/Si substrates via sol-gel methods. The microstructure, domain structure, ferroelectric, piezoelectric, magnetic properties as well as magnetoelectric coupling effect were investigated for the composite films at room temperature. Well-defined interfaces between GFO and BKNT layers and clear electric domain structures are observed. A strong magentoelectric effect is obtained with magnetoelectric voltage coefficient of α_E=30.89 mV/cm Oe, which is attributed to excellent ferroelectric, piezoelectric, and magnetic properties, as well as the coupling interaction between ferromagnetic GFO and ferroelectric BKNT phases for lead-free bilayer composite films. Besides, GFO and BKNT demonstrate the similar perovskite structure with well lattice matching, which endows the outstanding coupling and fascinating magnetoelectric properties. The present work opens up the opportunity of lead-free magnetoelectric composite films for both further fundamental studies and practical device applications such as sensors, transducers and multistate memories.     

Regulating crystal structure and ferroelectricity in Sr doped HfO2 thin films fabricated by metallo-organic decomposition

HfO₂ based binary ferroelectric oxides are promising candidate for nonvolatile memory devices due to their compatibility with the current Si-based technology. In this work, Sr doped HfO₂ (Sr:HfO₂) ferroelectric thin films with Sr concentration from 0% to 10?mol% were prepared on the platinum electrodes by metallo-organic decomposition (MOD). It was demonstrated that uniform Sr:HfO₂ thin films with extremely low roughness can be achieved and crystallized by MOD under a 700?°C annealing process. A wake-up stage was believed more essential for the ferroelectricity of the MOD derived Sr:HfO₂ thin film, since the remnant polarization of 13.3 µC/cm² and high dielectric constant of 30 were obtained after 10⁵ cycling tests. The transformation from monoclinic phase to cubic phase was observed with increasing the Sr concentration and the thickness of the films. X-ray photoelectron spectroscopy analysis confirmed the bonding type of O-Hf-O and O-Sr-O bonds in the film. The microscopic crystal structure of ferroelectric orthorhombic phase was observed by high resolution transmission electronic microscope. The intrinsic ferroelectricity of Sr:HfO₂ film was demonstrated by the hysteresis polarization-voltage loops and distinct current peaks in the current-voltage curve. Stable domain structure and its switching dynamics were monitored by piezoresponse force microscopy, indicating the native polarization of Sr:HfO₂. This work will provide a controllable routine to fabricate ferroelectric HfO₂ based thin films using MOD method.     

Dielectric,ferroelectric, and photoluminescent properties of Sm-doped Bi4Ti3O12 thin films synthesized by sol-gel method

We report on the structure, dielectric, ferroelectric, and photoluminescent properties of Sm³⁺-doped Bi₄Ti₃O₁₂ thin films which were prepared on fused silica and Pt/Ti/SiO₂/Si substrates by sol-gel method. The X-ray diffraction analysis confirmed that the Bi_4-xSm_xTi₃O₁₂ (BSmT) thin films were well crystallized in layered perovskite structure without any secondary phase. Raman spectra indicated that the structure of BSmT thin films was significantly distorted because of the Sm³⁺ doping. An appropriate doping amount of Sm³⁺ ions leads to obvious enhancement in ferroelectric and dielectric properties of BSmT thin films due to structure distortion and reduction in defects. In addition, the BSmT thin films also show orange-red color emission at 601?nm and long florescence lifetime (> 0.6?ms). This study indicated that lead-free BSmT thin films, which are featuring good electrical and photoluminescent properties, may have potential applications in integrated optoelectronic devices.     

Effect of Y concentration and film thickness on microstructure and electrical properties of HfO2 based thin films

In this work, we introduced a simple solution processing method to prepare yttrium (Y) doped hafnium oxide (HfO₂) based dielectric films. The films had high densities, low surface roughness, maximum permittivity of about 32, leakage current < 1.0 × 10^?7 A/cm² at 2 MV/cm, and breakdown field >5.0 MV/cm. In addition to dielectric performance, we investigated the influence of YO_1.5 fraction on the electronic structure between Y doped HfO₂ thin films and silicon (Si) substrates. The valence band electronic structure, energy gap and conduction band structure changed linearly with YO_1.5 fraction. Given this cost-effective deposition technique and excellent dielectric performance, solution-processed Y doped HfO₂ based thin films have the potential for insulator applications.     

Enhanced photovoltaic properties of PbTiO3-based ferroelectric thin films prepared by a sol-gel process

PbTiO₃ (PTO), Pb(Mn_0.1Ti_0.9)O₃ (PMTO), Pb(Sr_0.1Ti_0.9)O₃ (PSTO), and Pb(Zr_0.1Ti_0.9)O₃ (PZTO) were prepared on an indium tin oxide (ITO)/glass substrate by a sol-gel method. PTO, PMTO, PSTO, and PZTO films exhibited energy band gaps of 3.55 eV, 3.63 eV, 3.59 eV, and 3.66 eV, respectively. All these films generated high photocurrents due to high shift currents, because carrier migration channels were successfully introduced by a lattice mismatch between the films and ITO substrates. The PMTO thin film exhibited the best ferroelectric and photovoltaic properties, with a photovoltage of 0.74 V, a photocurrent density of 70 μA/cm², and a fill factor of 43.34%, which confirms that shift current and ferroelectric polarization are two main factors that affect the ferroelectric photovoltaic properties. The PSTO, PZTO, and PTO thin films displayed space-charge-limited current (SCLC) when the electric field strength was below 10 kV/cm, and these three films broke down when the electric field strength was above 10 kV/cm. Analysis of the shift current mechanism confirmed that the breakdown of the PZTO and PSTO thin films resulted from Pool Frenkel emission current. The PMTO thin film displayed SCLC in the test range, which indicates that doping with Mn could inhibit defect formation in ferroelectric thin films.     

Effect of sintering temperature on the ferroelectric property and electrocaloric effect of Pb0.8Ba0.2ZrO3 ceramics

This work presents the effects of sintering temperature ranging from 1200 °C to 1300 °C at intervals of 20 °C on the crystal structure, ferroelectric properties, and electrocaloric effect (ECE) of Pb_0.8Ba_0.2ZrO₃. Samples sintered at 1240 °C, 1260 °C, and 1280 °C have large remanent polarization and small coercive field. Meanwhile, samples sintered at 1260 °C, 1280 °C, and 1300 °C possess large breakdown field strength. Samples sintered at 1260 °C for 4 h exhibit the optimal ferroelectric properties. Antiferroelectricity-ferroelectricity (AFE-FE) phase transition occurs at room temperature T₁ (279 K). Directly examining ECE at this temperature is meaningful, and the temperature change is 0.068 K at approximately 60 °C and 30 kV/cm. Results laid the foundation for studying the performance of ferroelectric and ECE within this phase-transition temperature range and provide a reference for new solid-state refrigeration technology.     

Constraint Annealing of HfO2 Films on Silicon Substrate: Suppression of Si Outward Emission

Flexural tensile and compressive constraints were applied mechanically to the 7.5 nm thick HfO₂ films on Si substrates to investigate the influences of stress on the Si outward emission behavior in Si/HfO₂ during annealing. The constraint stress inhibited further growth of the interfacial layer (IL) between HfO₂ and Si, suppressing the IL‐growth‐induced Si outward emission. This fact was associated with atomic rearrangement that was induced during constrained annealing, resulting in the formation of a robust HfO₂ layer with low oxygen vacancy. Such an HfO₂ layer effectively suppressed the inward diffusion of oxygen, the IL growth and the Si out‐diffusion.     

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.     

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.     

Effect of (Zn,Mn) co-doping on the structure and ferroelectric properties of BiFeO3 thin films

BiFe_1-2xZn_xMn_xO₃ (BFZMO, with x = 0–0.05) thin films were synthesized via sol–gel method. Effects of (Zn, Mn) co-doping on the structure, ferroelectric, dielectric, and optical properties of BiFeO₃ (BFO) films were investigated. BFZMO thin films exhibit rhombohedral structure. Scanning electron microscopy (SEM) images indicate that co-doping leads to a decrease in grain size and number of defects. Leakage current density (4.60 × 10^?6 A/cm²) of BFZMO film with x = 0.02 was found to be two orders of magnitude lower than that of pristine BFO film. Owing to decreased leakage current density, saturated P–E curves were obtained. Maximum double remnant polarization of 413.2 μC/cm² was observed for BFZMO thin film with x = 0.02, while that for the BFO film was found to be 199.68 μC/cm². The reason for improved ferroelectric properties is partial substitution of Fe ions with Zn and Mn ions, which resulted in a reduction in the effect of oxygen vacancy defects. In addition, co-doping was found to decrease optical bandgap of BFO film, opening several possible routes for novel applications of these (Zn, Mn) co-doped BFO thin films.     

Structural and electrical properties of the sol-gel derived multiferroic BiFeO3 monolayer and NiTiO3-BiFeO3 bilayer thin films

In this paper, the multiferroic BeFiO₃ monolayer and NiTiO₃–BiFeO₃ bilayer thin films were fabricated by spin-coating method on the SrRuO₃/n⁺-Si substrate. The structural and ferroelectric properties of multiferroic BeFiO₃ monolayer and NiTiO₃–BiFeO₃ bilayer thin films were investigated. Both multiferroic films showed the typical XRD patterns of the perovskite structure without presence of the second phase. The electrical properties, such as leakage current and remnant polarization, of the NiTiO₃–BiFeO₃ bilayer film were superior to those of BeFiO₃ monolayer film, which those values were 1.94 × 10⁻⁴ A/cm² at electric field of 0.75 MV/cm and 14.05 μC/cm², respectively. This outcome is due to the NiTiO₃–BiFeO₃ bilayer film with a high Schottky barrier height as well as a top NiTiO₃ layer on the BiFeO₃ film inducing the strain-induced polarization rotation and forming the strong domain-wall pinning.     

Thermal treatment effect on the magnetoelectric properties of (Ni0.5Zn0.5)Fe2O4/Pt/Pb(Zr0.3Ti0.7)O3 heterostructured thin films

Magnetoelectric (ME) property modulation in heterostructured (Ni_0.5Zn_0.5)Fe₂O₄/Pt/Pb(Zr_0.3Ti_0.7)O₃ (NZFO/Pt/PZT) thin films on platinized Si substrate by thermal annealing condition variation was studied. In an attempt to prevent interfacial reaction between NZFO and PZT layers during high temperature annealing, thin Pt layer was deposited which can serve as inter-diffusion barrier as well as electrode. The ferroelectric, magnetic, and ME properties of the heterostructured film were noticeably modulated due to microstructural evolution and clamping relaxation developed during thermal annealing process. Room temperature ME voltage coefficient of the heterostructured thin films was enhanced with increasing annealing temperature and reached to 29 mV/cm·Oe when annealed at 650 °C.