Enhanced ferroelectric and improved leakage of BFO-based thin films through increasing entropy strategy

BiFeO_(3)(BFO)has received considerable attention as a lead-free ferroelectric film due to its large theoretical remnant polariza-tion.However,BFO suffers from a large leakage current,resulting in poor ferroelectric properties.Herein,the sol-gel method was used to deposit a series of BFO-based thin films on fluorine-doped tin oxide substrates,and the effects of the substitution of the elements Co,Cu,Mn(B-site)and Sm,Eu,La(A-site)on the crystal structure,ferroelectricity,and leakage current of the BFO-based thin films were invest-igated.Results confirmed that lattice distortion by X-ray diffraction can be attributed to the substitution of individual elements in the BFO-based films.Sm and Eu substitutions contribute to the lattice distortion in a pseudo-cubic structure,while La is biased toward pseudo-tet-ragonal.Piezoelectric force microscopy confirmed that reversible switching of ferroelectric domains by nearly 180°can be realized through the prepared films.The ferroelectric hysteresis loops showed that the order for the polarization contribution is as follows:Cu>Co>Mn(B-site),Sm>La>Eu(A-site).The current density voltage curves indicated that the order for leakage contribution is as follows:Mn<Cu<Co(B-site),La<Eu<Sm(A-site).Scanning electron microscopy showed that the introduction of Cu elements facilitates the formation of dense grains,and the grain size distribution statistics proved that La element promotes the reduction of grain size,leading to the increase of grain boundaries and the reduction of leakage.Finally,a Bi_(0.985)Sm_(0.045)La_(0.03)Fe_(0.96)Co_(0.02)Cu_(0.02)O_(3)(SmLa-CoCu)thin film with a qualitative leap in the remnant polarization from 25.5(Bi_(0.985)Sm_(0.075)FeO_(3))to 98.8µC/cm^(2)(SmLa-CoCu)was prepared through the syner-gistic action of Sm,La,Co,and Cu elements.The leakage current is also drastically reduced from 160 to 8.4 mA/cm^(2)at a field strength of 150 kV/cm.Thus,based on the increasing entropy strategy of chemical engineering,this study focuses on enhancing ferroelectricity and decreasing leakage current,providing a promising path for the advancement of ferroelectric devices.

Structure,ferroelectric,and enhanced fatigue properties of sol–gel-processed new Bi-based perovskite thin films of Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)

Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties.New Bi-based perovskite thin films Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)(BCT–PT) are deposited on Pt(111)/Ti/SiO_(2)/Si substrates in the present study by the traditional sol–gel method.Their structures and related ferroelectric and fatigue characteristics are studied in-depth.The BCT–PT thin films exhibit good crystallization within the phase-pure perovskite structure,besides,they have a predominant(100) orientation together with a dense and homogeneous microstructure.The remnant polarization(2P_(r)) values at 30 μC/cm^(2) and 16 μC/cm^(2) are observed in 0.1BCT–0.9PT and 0.2BCT–0.8PT thin films,respectively.More intriguingly,although the polarization values are not so high,0.2BCT–0.8PT thin films show outstanding polarization fatigue properties,with a high switchable polarization of 93.6% of the starting values after 10^(8) cycles,indicating promising applications in ferroelectric memories.

Optimal parameter space for stabilizing the ferroelectric phase of Hf_(0.5)Zr_(0.5)O_(2) thin films under strain and electric fields

Hafnia-based ferroelectric materials, like Hf_(0.5)Zr_(0.5)O_(2)(HZO), have received tremendous attention owing to their potentials for building ultra-thin ferroelectric devices. The orthorhombic(O)-phase of HZO is ferroelectric but metastable in its bulk form under ambient conditions, which poses a considerable challenge to maintaining the operation performance of HZO-based ferroelectric devices. Here, we theoretically addressed this issue that provides parameter spaces for stabilizing the O-phase of HZO thin-films under various conditions. Three mechanisms were found to be capable of lowering the relative energy of the O-phase, namely, more significant surface-bulk portion of(111) surfaces, compressive c-axis strain,and positive electric fields. Considering these mechanisms, we plotted two ternary phase diagrams for HZO thin-films where the strain was applied along the in-plane uniaxial and biaxial, respectively. These diagrams indicate the O-phase could be stabilized by solely shrinking the film-thickness below 12.26 nm, ascribed to its lower surface energies. All these results shed considerable light on designing more robust and higher-performance ferroelectric devices.

Influence of pyrolysis temperature on ferroelectric properties of La and Mn co-doped BiFeO_3 thin films

Bi0.9La0.1Fe0.95Mn0.05O3 （BLFMO） ferroelectric thin films were fabricated on Pt/Ti/SiO2/Si/ substrates by the sol-gel process at different pyrolysis temperatures. The mass loss of BLFMO powder was investigated by thermo gravimetry analyser （TGA）, and the polycrystalline structure and smooth surface of BLFMO thin films were characterized by X-ray diffraction （XRD） and atomic force microscopy （AFM）, respectively. The remnant polarization （Pr） of the BLFMO films pyrolyzed at 420 ℃ is 21.2 μC/cm2 at the coercive field （Ec） of 99 kV/cm and the leakage current density is 7.1×10-3 A/cm2, which indicates that the BLFMO thin films display relatively good ferroelectric property at this temperature.

Effects of Thickness and Anisotropic Strain on Polarization Switching Properties of Sub-10nm Epitaxial Hf_(0.5)Zr_(0.5)O_(2)Thin Films

Doped HfO_(2)-based ferroelectric(FE)films are emerging as leading contenders for next-generation FE nonvolatile memories due to their excellent compatibility with complementary metal oxide semiconductor processes and robust ferroelectricity at nanoscale dimensions.Despite the considerable attention paid to the FE properties of HfO_(2)-based films in recent years,enhancing their polarization switching speed remains a critical research challenge.We demonstrate the strong ferroelectricity of sub-10nm Hf_(0.5)Zr_(0.5)O_(2)(HZO)thin films and show that the polarization switching speed of these thin films can be significantly affected by HZO thickness and anisotropically strained La_(0.67)Sr_(0.33)MO_(3)-buffered layer.Our observations indicate that the HZO thin film thickness and anisotropically strained La_(0.67)Sr_(0.33)MO_(3)layer influence the nucleation of reverse domains by altering the phase composition of the HZO thin film,thereby reducing the polarization switching time.Although the increase in HZO thickness and anisotropic compressive strain hinder the formation of the FE phase,they can enable faster switching.Our findings suggest that FE HZO ultrathin films with polar orthorhombic structures have broad application prospects in microelectronic devices.These insights into novel methods for increasing polarization switching speed are poised to advance the development of high-performance FE devices.

Enhancement of photoelectrochemical performance in ferroelectric films via the introduction of an Au buffer layer

The inefficient separation of photogenerated carriers has become a serious problem that limits the photoelectrochemical(PEC)performance of semiconductors.Herein,a sol-gel method was used to prepare BiFeO_(3) ferroelectric thin films with FTO and FTO/Au as substrates,respectively.The polarization electric field of the ferroelectric can more effectively separate the carriers generated in the photoelectrode.Meanwhile,the introduction of an Au buffer layer can reduce the resistance in the process of charge transfer,accelerate the carrier migration,and enhance the efficiency of the charge separation.Under light irradiation,Au/BiFeO_(3) photoelectrode exhibited an extraordinary improvement in PEC water splitting compared with BiFeO_(3).In addition,the ferroelectric polarization electric field causes band bending,which further accelerates the separation of electrons and holes and improves the PEC performance of the photoelectrode.This work promotes the effective application of ferroelectric films in PEC water splitting.

Study of Depolarization Field Influence on Ferroelectric Films Within Transverse Ising Model

An improved transverse Ising model is proposed by taking the depolarization field effect into account. Within the framework of mean-held theory we investigate the behavior of the ferroelectric thin film. Our results show that the influence of the depolarization field is to flatten the spontaneous polarization profile and make the films more homogeneous, which is consistent with Ginzburg Landau theory. This fact shows that this model can be taken as an effective model to deal with the ferroelectric film and can be further extended to refer to quantum effect. The competition between quantum effect and depolarization field induces some interesting phenomena on ferroelectric thin films.

Effect of Annealing on Ferroelectric Properties of Bi_ (3.25)La_(0.75)Ti_3O_ (12) Thin Films Prepared by the Sol-gel Method

Bi3.25La0.75Ti3O12（BLT）thin films were prepared on Pt/Ti/SiO2/Si substrate by the sol-gel method.The effect of annealing on their structures and ferroelectric properties was investigated.The XRD patterns indicate that the BLT films annealed at different temperatures are randomly orientated and the single perovskite phase is obtained at 550℃.The remmant polarization increnses and the coercive field decreases with the annealing temperature increasing.The leakage current density of the BLT films annealed at 700℃ is about 5.8×10^-8A/cm^2 at the electrie field of 250kv/cm.

Ferroelectric properties of sol-gel derived Nd-doped SrBi_4Ti_4O_(15) thin films

Neodymium-doped strontium bismuth titanate （SrBi4-xNdxTi4O15） ferroelectric thin films were fabricated using the sol-gel method on Pt/Ti/SiO2/Si substrates. The influence of Nd content on the microstructure and ferroelectric properties of SrBi4-xNdxTi4O15 thin films were systematically studied. The results indicated that the SrBi3.88Nd0.12Ti4O15 （SBNT0.12） thin films had better ferroelectric properties, with a remanent polarization of （2Pr） of 34.3 μC/cm^2 and a coercive field （2Ec） of 220 kV/cm. This could be attributed to the fact that SBNT0.12 ferroelectric thin films consisted of more and larger ball-like grains, approximately 150-200 nm, with structure distortion, which greatly contributed to the improvement of the ferroelectric properties of the films. Furthermore, the film exhibited a good fatigue resistant property. The value of 2Pr after 10^10 switching cycles did not change significantly. The SrBi3.88Nd0.12Ti4O15 films were promising candidates for the application of FeRAMs.

Tuning of Optical Properties via Annealing of Bismuth Ferrite (BiFeO3) Thin Films

In this study we are reporting annealing induced optical properties of bismuth ferrite (BiFeO3) thin films deposited on glass substrate via spin coating at 5000 rpm. The structural, optical and surface morphology of BiFeO3 (BFO) thin films have been studied via X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Optical absorption (UV-Vis) and Photoluminescence (PL) spectroscopy. XRD spectra confirm annealing induced phase formation of BiFeO3 possessing a rhombohedral R3c structure. The films are dense and without cracks, although the presence of porosity in BFO/glass was observed. Moreover, optical absorption spectra indicate annealing induced effect on the energy band structure in comparison to pristine BiFeO3. It is observed that annealing effect shows an intense shift in the UV-Vis spectra as diffuse absorption together with the variation in the optical band gap. The evaluated optical band gap values are approximately equal to the bulk band gap value of BiFeO3.

Effect of crystallization temperature on microstructure and ferroelectric property of Bi_(3.25)Eu_(0.75)Ti_3O_(12) thin films prepared by MOD method

Europium-substituted bismuth titanate (Bi3.25Eu0.75Ti3O12) thin films were deposited on the Pt/Ti/SiO2/Si(111) substrates by metal-organic decomposition (MOD) method using a repeated coating/drying cycle. Effect of crystallization temperature on microstructure of Bi3.25Eu0.75Ti3O12(BET) thin films was investigated by X-ray diffractometry(XRD), scanning electron microscopy (SEM) and Raman spectroscopy, and ferroelectric property was studied by Precision Workstation Ferroelectric Tester. The crystallinity of BET thin films is improved and the average grain size increases with the crystallization temperature from 600 to 750 ℃. Under 9 V applied voltage, the remnant polarization (2Pr) of BET thin films annealed at 700 ℃ is 50.7 μm/cm2, which is higher than that of the films annealed at 600, 650 and 750℃.

Effect of electromechanical the properties of epitaxial boundary conditions on ferroelectric thin films

The effects of internal stresses and depolarization fields on the properties of epitaxial ferroelectric perovskite thin films are discussed by employing the dynamic Ginzbur~Landau equation （DCLE）. The numerical solution for BaTiO3 film shows that internal stress and the depolarization field have the most effects on ferroelectric properties such as polarization, Curie temperature and susceptibility. With the increase of the thickness of the film, the polarization of epitaxia] ferroelectric thin film is enhanced rapidly under high internal compressively stress. With the thickness exceeding the critical thickness for dislocation formation, the polarization increases slowly and even weakens due to relaxed internal stresses and a weak electrical boundary condition. This indicates that the effects of mechanical and electrical boundary conditions both diminish for ferroelectric thick films. Consequently, our thermodynamic method is a full scale model that can predict the properties of ferroelectric perovskite films in a wide range of film thickness.

Remarkable Improvement of Ferroelectric Properties and Leakage Current in BiFeO_3 Thin Films by Nd Modification

Ferroelectric and leakage properties are important for ferroelectric applications. Pure and Nd-doped（x=0.05-0.20） BiFeO3 thin films were fabricated by sol-gel method on FTO substrates. The phase structure, surface morphology, leakage current, ferroelectric properties, and optical properties of BiFeO3-based thin films were investigated. The substitution of Nd^3＋ ions for the Bi^3＋ site converts the structure from rhombohedral to coexisting tetragonal and orthorhombic. Nd doping improves the crystallinity of BiFeO3 thin films. The leakage current of Nd-doped BiFeO3 decreases by two to three orders of magnitude compared with that of pure BiFeO3. Among the samples, 15% Nd-doped BiFeO3 exhibits the strongest ferroelectric polarization of 17.96 μC/cm^2. Furthermore, the absorption edges of Bi1-xNdxFeO3 thin films show a slight red-shift after Nd doping.

MINIMUM SIZE OF 180 DEGREE DOMAINS IN FERROELECTRIC THIN FILMS COVERED BY ELECTRODES

Ferroelectric domain switching under low voltage or short pulses is of interest for the development of high-density random access memory （FRAM） devices. Being necessarily very small in size, instability and back switching often occur when the external voltage is removed, which creates serious problems. In this investigation, a general approach to determine the minimum size of ferroelectric domain to avoid back switching was developed, and as an example, a 180° domain in a ferroelectric thin film covered by the upper and lower electrodes was considered in detail. We note that our approach is generally applicable to many other fields, including phase transformation, nucleation and expansion of dislocation loops in thin films, etc.

Effect of Annealing Temperature on the Ferroelectric Properties of BiFeO_3 Thin Films Prepared by Sol-gel Process

Sol-gel process was adopted to prepare BiFeO3 films.BiFeO3 films were deposited on LaNiO3 coated Si（100） substrates annealed at 500 and 550 ℃,respectively.The X-ray diffraction results reveal that BiFeO3 film has a rhombohedrally distorted perovskite structure with space group R3c.The film annealed at 500 ℃ has larger remnant polarization（Pr） of 35.3 μC/cm2.For the film annealed at 550 ℃,smaller remnant polarization of Pr=4.8 μC/cm^2 is observed for its low breakdown electric field.Lower leakage conduction is observed in the film annealed at 500 ℃ at low applied field.

Orientation of Bi_(3.2)La_(0.8)Ti_3O_(12) Ferroelectric Thin Films with Different Annealing Schedules

Fatigue-free Bi3.2La0.8Ti3O12 ferroelectric thin films were successfully prepared on p-Si （100） substrates using metalorganic solution deposition process. The orientation and formation of 5-layers thin films were studied under different processing conditions using XRD. Experimental results indicate that increase in annealing time at 700 ℃ after preannealing for 10 min at 400 ℃ can remarkably increase （200）-orientation of the films derived from the precursor solutions with two contents of citric acid. Meanwhile, high content of citric acid increases the film thickness and is conducive to the α-orientation of the films with the preannealing, and low concentration of the solution is conducive to the c-orientation of the films without the preannealing.

THE STABILITY INVESTIGATION OF FERROELECTRIC SrBi_2Ta_2O_9 THIN FILMS ANNEALED IN FORMING GAS

The hysteresis loop changes of ferroelecric SrBi_2 Ta_2 O_9 (SBT) thin films(330nm) us the temperature of forming gas (5 percent hydrogen+95 percent nitrogen) annealing weremeasured when the annealing time was 1min and 10min. The selected annealing temperature was at 100deg C,200 deg C 250 deg C, 300 deg C, 350 deg C,400 deg C and 450 deg C, respectively. Our resultsshowed that the ferroelectric properties were easily destroyed and the leakage current changedabruptly when the SBT thin films were in their ferroelectric phase (<270 deg C). The space chargesat the grain boundary may take an important role' in absorption polarity molecular hydrogen when theSBT thin films were in the ferroelectric phase. The oxygen recovery experiments were also performedand investigated in this work.

Effect of La Doping on Microstructure and Ferroelectric Prop-erties of Bi_4Ti_3O_(12) Thin Films Prepared by Sol-gel Method

The Bi4Ti3Oi2 and Bi3.25La0.75Ti3O12 thin films were prepared on the Pt/Ti/SiO2/Si substrate using the sol-gel method. The effect of La doping on the microstructure and ferroelectric properties of Bi4Ti3O12 films were investigated. Both the Bi4Ti3O12 and Bi3.25La0.75Ti3O12 thin films exhibited typical bismuth layered perovskite structure. The 2Pr （remanent polarization） value of Bi3.25La0.75Ti3O12 thin films is 18.6 μC/cm^2, which is much larger than that of Bi4Ti3O12 thin films. And the Bi3.2eLa0.75Ti3O12 films show fatigue-free behavior, while the Bi4Ti3O12 thin films exhibit the fatigue problem. The mechanism of improvement of La doping was discussed.

Size Effects of the Critical Temperature in Ferroelectric Thin Films

The size effects of the critical behaviors for the systems of interacting spins are discussed extensively inliterature.In this paper,the finite-size dependence of the critical temperature and susceptibility of the ferroelectric thinfilm are investigated numerically based on the four-state Potts model with the nearest-neighbor interactions between thedipole moments.The four orientations of the domains exist in the ferroelectric film and the movement of the domainwalls determines the polarization switching process besides the boundary conditions of the film.The critical exponentsare obtained and our investigations show that the boundary conditions play the important roles for the ferroelectricproperties of the thin films and the critical behavior of the thin films strongly depends on the feature of the surface.