Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

DFT study of structural, electronic and vibrational properties of pure (Al2O3)n (n = 9, 10, 12, 15) and Ni-doped (Al2O3)n (n = 9, 10) clusters

The geometrical, electronic and vibrational properties of pure (Al₂O₃)_n (n = 9, 10, 12, 15) clusters and Ni-doped (Al₂O₃)_9-10 clusters are investigated by density functional theory. There are four different Ni-doped (Al₂O₃)₉ clusters and one Ni-doped (Al₂O₃)₁₀ cluster taken into account. Compared with the pure clusters, the Ni-doped (Al₂O₃)_9-10 clusters have narrower HOMO-LUMO energy gaps. The results indicate that the impurity of Ni atom is mainly responsible for the reduction of the HOMO-LUMO energy gap. One characteristic vibration band at about 1030 cm⁻¹ is found in the vibrational frequencies of the Ni-doped (Al₂O₃)_9-10 clusters, which is caused by the asymmetric Al-O-Al stretching vibration. Another band at around 826 cm⁻¹ involving the characteristic vibration of Ni-O bond is in good agreement with experimental results.     

Enhanced dielectric and ferroelectric properties of Pb1−3x/2Lax(Zr0.5Ti0.5)O3 thin films with low lanthanum substitution

Effects of lanthanum (La) substitution (0.003 ≤ x ≤ 0.015) on the dielectric and ferroelectric properties of Pb(Zr_0.5Ti_0.5)O₃ thin films have been investigated. The films were synthesized on the Pt (1 1 1)/Ti/SiO₂/Si (1 0 0) substrates by a sol-gel method. Large dielectric constants of the films are obtained within range of 800-1600 which are almost comparable to those observed in bulk ceramics. The films also show improved remnant polarization values and reduced coercive field values with the increasing addition of La substitution. Our results suggest that low La substitution contributes to enhance film electric properties due to the improvement of non-180° domain wall mobility as well as the stabilization of tetragonal phase.     

The crystalline orientation and ferroelectric properties of Bi3.25La0.75Ti3O12 thin films mediated by the intermediate layer of LaNiO3

c-Axis-oriented and (1 1 7)-oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films are successfully controlled by the intermediate layer of LaNiO₃ (LNO) with chemical solution deposition (CSD), respectively. X-ray diffraction (XRD) demonstrates that the structure and orientation of LNO thin films have a strong effect on the orientation of BLT thin films. Scanning electron microscopy suggests that BLT thin films on LNO electrode exhibit crack-free, uniform size grains and dense microstructure. A crystalline orientation dependent remanent polarization is observed in BLT thin films, and it is found that the remanent polarization (2P_r) of (1 1 7)-oriented films is larger than that of c-axis-oriented films. Our research directly demonstrates that the vector of the main spontaneous polarization in these layered perovskite materials (BLT) is along a-axis.     

Phase compositions and ferroelectric properties of Pb(Zr0.52,Ti0.48)O3 thin films with different highly orientations prepared by a sol-gel route

It is shown that different highly oriented Pb(Zr_0.52,Ti_0.48)O₃ films can be obtained on Pt/Ti/SiO₂/Si substrate using a sol-gel technique. The effects of pyrolysis temperature on the orientation, phase composition and ferroelectric properties of the films are investigated. It is found the ferroelectric hysteresis loops of (1 1 1)-oriented film, (1 1 1) and (1 0 0) mix-oriented film can both be saturated when the external electric field is large enough, whereas the hysteresis loop of (1 0 0)-oriented film is difficult to saturate. The analysis of X-ray diffraction indicated the possibility of different phase composition in different oriented films under large film residual stress. Higher remnant polarization (53 μC/cm²) for (1 0 0)-oriented film can be attributed to its more tetragonal phase composition, which results in that the in-plane domain switching can continuously occur with external electric field increasing.     

Mn:BiFeO3/Zn:BiFeO3 bilayered thin films of (1 1 1) orientation

Ferroelectric and fatigue behavior of bilayered thin films consisting of Mn⁴⁺-modified BiFeO₃ and Zn²⁺-modified BiFeO₃, which were deposited on SrRuO₃-buffered Pt coated silicon substrates, were systematically investigated. The (1 1 1) orientation is induced for the BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer, due to the introduction of the bottom BiFe_0.95Zn_0.05O₃ layer. With increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer, their leakage current decreases, and the fatigue endurance is greatly improved owing to the introduction of the BiFe_0.95Mn_0.05O₃ layer with a lower fatigue rate. The BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer with the thickness ratio of 3:1 exhibits a larger remanent polarization of 2P_r ∼ 161.0 μC/cm² than those of bilayers with different thickness ratios, while their coercive field slightly increases with increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer.     

The ferroelectric and ferromagnetic characterization of CoFe2O4/Pb(Mg1/3Nb2/3)O3-PbTiO3 multilayered thin films

The multiferroic (PMN-PT/CFO)_n (n = 1,2) multilayered thin films have been prepared on SiO₂/Si(1 0 0) substrate with LNO as buffer layer via a rf magnetron sputtering method. The structure and surface morphology of multilayered thin films were determined by X-ray diffraction (XRD) and atom force microscopy (AFM), respectively. The smooth, dense and crack-free surface shows the excellent crystal quality with root-mean-square (RMS) roughness only 2.9 nm, and average grain size of CFO thin films on the surface is about 44 nm. The influence of the thin films thickness size, periodicity n and crystallite orientation on their properties including ferroelectric, ferromagnetic properties in the (PMN-PT/CFO)_n multilayered thin films were investigated. For multilayered thin films with n = 1 and n = 2, the remanent polarization Pr are 17.9 μC/cm² and 9.9 μC/cm²; the coercivity H_c are 1044 Oe and 660 Oe, respectively. In addition, the relative mechanism are also discussed.     

Role of crystal orientation on the magnetic properties of CoFe2O4 thin films grown on Si (1 0 0) and Al2O3 (0 0 0 1) substrates using pulsed laser deposition

We report the influence of crystal orientation on the magnetic properties of CoFe₂O₄ (CFO) thin films grown on single crystal Si (1 0 0) and c-cut sapphire (Al₂O₃) (0 0 0 1) substrates using pulsed laser deposition technique. The thickness was varied from 200 to 50 nm for CFO films grown on Si substrates, while it was fixed at 200 nm for CFO films grown on Al₂O₃ substrates. We observed that the 200 and 100 nm thick CFO-Si films grew in both (1 1 1) and (3 1 1) directions and displayed out-of-plane anisotropy, whereas the 50 nm thick CFO-Si film showed only an (1 1 1) orientation and an in-plane anisotropy. The 200 nm thick CFO film grown on an Al₂O₃ substrate was also found to show a complete (1 1 1) orientation and a strong in-plane anisotropy. These observations pointed to a definite relation between the crystalline orientation and the observed magnetic anisotropy in the CFO thin films.     

Electrical transport properties of Fe3−xCrxO4 ferrite films on MgO (0 0 1) grown by molecular beam epitaxy

In this report, we fabricated a series of Fe_3−xCr_xO₄(0≦x≦2) films by plasma-oxygen-assisted molecular beam epitaxy (MBE) and did structural and electrical characterizations of these films. These films show textured single phase quality and the lattice parameters are consistent with those of the bulk at low Cr composition (x<0.9). However, the lattice parameters show severe deviation from the bulk value in the intermediate region of 0.9≦x≦1.5 and no diffraction can be resolved at x∼2. These discrepancies may be attributed to the cation distributions and the instability of spinal structure as Cr concentration becomes dominant. The resistivity presents a typical Arrhenius temperature dependence with ρ=ρ₀ exp (E_p/k_BT) indicating that the transport is due to a hopping mechanism. The prefactor ρ₀ increases in Fe_3−xCr_xO₄, at smaller x but tends to level out for x>1, suggesting that Cr³⁺ ions may start to replace Fe³⁺ ions at the A site in the high x region. The activation energy of electrical hopping gradually increases at low Cr concentration but abruptly rises to ∼110 meV at x>0.9, suggesting a crossover from electron-hopping mediated transport to a thermally activated band gap excitation.     

Crystal orientation dependence of the in-plane dielectric properties for Ba(Sn0.15Ti0.85)O3 thin films

Barium tin titanate Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films with (1 0 0), (1 1 0) and (1 1 1) orientation were grown on (1 0 0), (1 1 0) and (1 1 1) LaAlO₃ (LAO) single-crystal substrates through sol–gel process, respectively. The in-plane dielectric properties of the films were measured on interdigital capacitor (IDC). Films with the (1 1 1) orientation had larger relative dielectric constant and larger tunability against the dc bias electric field than (1 0 0)- and (1 1 0)-oriented films. This difference in dielectric properties in these three kinds of oriented BTS films may be attributed due to change in the direction and magnitude of electric polarization in orientation engineered BTS films. This work clearly reveals the dielectric properties of BTS films exhibited a strong sensitivity to crystal orientation.     

Nonmonotonic variation of magnetization in Bi0.8La0.2−xPbxFeO3 (0≤x≤0.2) multiferroics

Systematic studies of crystalline structure, magnetic and ferroelectric properties have been performed on polycrystalline Bi_0.8La_0.2−xPb_xFeO₃ ceramic samples, in which x changes continuously from 0 to 0.2. Rietveld refinement of the x-ray diffraction (XRD) patterns shows that the compound crystal structure changes gradually from pseudotetragonal to pseudocubic with increasing Pb concentration. Coupled with the structural and compositional changes, magnetic ordering of the samples exhibits significantly non-monotonical variation corresponding to x. The compound remnant magnetization (M_r) and coercivity (H_c) both reach minimum values close to zero at x=0.07. This variation of magnetic property in co-doped samples can be attributed to the extent of suppression of cycloid spin structure in original BiFeO₃ with changing x. Unlike magnetic responses, the ferroelectric measurements show that the compounds have monotonical change in the remnant electric dipole polarization (P_r).     

Study of the [(Co45Fe45Zr10)x(Al2O3)100−x/a-Si:H]m multilayer nanostructure by polarized neutron reflectometry

Polarized neutron reflectometry was used to investigate the amorphous multilayer nanostructures [(Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100−x/a-Si:H]_m, whose magnetic properties are dependent on the concentration of the magnetic constituent (x=34, 47 and 60 at%) as well as on the thicknesses of the metal-dielectric (Co₄₅Fe₄₅Zr₁₀)_x(Al₂O₃)_100−x and semiconductor a-Si:H layers. The average magnetization of the individual magnetic layer is found to be inhomogeneous with the magnetically active central part and two magnetically dead parts at the interfaces.     

Electrical and optical properties of thermally-evaporated thin films from A2[TiO(C2O4)2] (A = K, PPh4) and 1,8-dihydroxyanthraquinone

In this work, the synthesis of molecular materials formed from A₂[TiO(C₂O₄)₂] (A = K, PPh4) and 1,8 dihydroxyanthraquinone is reported. The synthesized materials were characterized by atomic force microscopy (AFM), infrared (IR) and ultraviolet-visible (UV-vis) spectroscopy. IR spectroscopy showed that the molecular-material thin-films, deposited by vacuum thermal evaporation, exhibit the same intra-molecular vibration modes as the starting powders, which suggests that the thermal evaporation process does not alter the initial chemical structures. Electrical transport properties were studied by dc conductivity measurements. The electrical activation energies of the complexes, which were in the range of 0.003-1.16 eV, were calculated from Arrhenius plots. Optical absorption studies in the wavelength range of 190-1090 nm at room temperature showed that the optical band gaps of the thin films were around 1.9-2.3 eV for direct transitions Eg_d. The cubic NLO effects were substantially enhanced for materials synthesized from K₂[TiO(C₂O₄)₂], where χ⁽³⁾ (−3ω; ω, ω, ω) values in the promising range of 10⁻¹² esu have been evaluated.     

Geometric and electronic structure of positively and negatively poled LiNbO3 (0 0 0 1) surfaces

The effect of ferroelectric poling direction on the structure and electronic properties of the LiNbO₃ (0 0 0 1) surface was characterized. Low energy and reflection high energy electron diffraction indicated that both the positively and negatively poled surfaces were (1 × 1) with no evidence of longer range periodic reconstructions. Low energy ion scattering spectra from both surfaces were dominated by scattering from oxygen atoms. X-ray and ultraviolet photoelectron spectra also showed little difference between the positively and negatively poled surfaces, with the exception of a high binding energy shoulder on the O 1s core level of the negative surface. Exposure of the surfaces to atomic hydrogen caused reduction of the surface Nb rather than an increase in intensity on the high binding energy side of the O 1s peak, indicating that the shoulder on the O 1s peak on the negative surface was not due to surface hydroxyl groups. Temperature programmed desorption measurements indicated that the nearly stoichiometric LiNbO₃ samples were susceptible to loss of Li₂O starting at temperatures as low as 500 K, independent of the poling direction. An adatom/vacancy model is proposed in which oxygen ad-anions accumulate on one side of the crystal while oxygen anion vacancies are created on the opposite surface. This model can explain the apparent oxygen termination of both surfaces and the observed (1 × 1) periodicity of the surfaces, and also effectively screens the thickness dependent electric field associated with the polar orientation of the crystal.     

Density functional study of TaSin (n = 1-3, 12) clusters adsorbed to graphene surface

A plane-wave density functional theory (DFT) calculations have been performed to investigate structural and electronic properties of TaSi_n (n = 1-3, 12) clusters supported by graphene surface. The resulting adsorption structures are described and discussed in terms of stability, bonding, and electron transfer between the cluster and the graphene. The TaSi_n clusters on graphene surface favor their free-standing ground-state structures. Especially in the cases of the linear TaSi₂ and the planar TaSi₃, the graphene surface may catalyze the transition of the TaSi_n clusters from an isomer of lower dimensionality into the ground-state structure. The adsorption site and configuration of TaSi_n on graphene surface are dominated by the interaction between Ta atom and graphene. Ta atom prefers to adsorb on the hollow site of graphene, and Si atoms tend to locate on the bridge site. Further, the electron transfer is found to proceed from the cluster to the surface for n = 1 and 2, while its direction reverses as n > 2. For the case of TaSi, chemisorption is shown to prevail over physisorption as the dominant mode of surface-adsorbate interaction by charge density analysis.     

Effect of Cr100−xTix (x = 0-19 at.%) alloy underlayers on the high coercivity of FePt thin film below the substrate temperature of 250 °C

The effect of Cr_100−xTi_x underlayer on orderd-L1₀ FePt films was investigated. A low-temperature ordering of FePt films could be attained through changing the Ti content of Cr_100−xTi_x underlayer. The ordering temperature of the 30 nm FePt film grown on 20 nm Cr₉₀Ti₁₀ underlayer was reduced to 250 °C which is practical manufacture process temperature. An in-plane coercivity was very high to 6000 Oe and a ratio of remnant magnetization (M_r) to saturation magnetization (M_s) was as large as 0.85. This result indicates that the coercivity obtained at 250 °C by the effect of CrTi underlayer is significantly higher than those obtained at 250-275 °C by the effect of underlayers in other conventional studies. The prominent improvement of the magnetic properties of ordered FePt thin films at low temperature of 250 °C could be understood with considering the strain-induced ordering phase transformation associated with lattice mismatch between Cr underlayer and FePt magnetic layer due to an addition of Ti content.     

Fabrication of the hydrogen resistive ferroelectric film of the (Pb0.72La0.28)Ti0.93O3/Pb(Zr0.52Ti0.48)O3/(Pb0.72La0.28)Ti0.93O3 heterostructure by a pulsed laser deposition method

(Pb_0.72La_0.28)Ti_0.93O₃ (PLT)/Pb(Zr_0.52Ti_0.48)O₃ (PZT)/PLT heterostructure was fabricated by using a pulsed laser deposition method. After depositing this structure, the hydrogen annealing process was performed in the forming gas (95% N₂ + 5% H₂) at a substrate temperature of 400 °C for 30 min to study the effects of hydrogen passivation.The heterostructure was not degraded by the hydrogen annealing in contrast with the case of PZT film without buffer layers. This heterostructure showed almost no degradation in terms of the remanent polarization even after the H₂ annealing, while the PZT film exhibited 64% reduction, which is from 20.1 to 7.3 μC/cm² after the annealing. The leakage current was decreased by an order in the case of the heterostructure, while the leakage current of the PZT film increased by an order.These can be explained that the PLT bottom buffer layer works as a seeing layer to help the PZT growth and the top PLT buffer layer acts as a barrier for penetrating hydrogen atoms.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

Molecular dynamics simulations of CFx (x = 2, 3) molecules at Si3N4 and SiO2 surfaces

Molecular dynamics simulations of the interaction between CF_x (x = 2, 3) molecules and crystalline as well as amorphous Si₃N₄ and SiO₂ surfaces using a density-functional based method are reported. The binding energies of various configurations at the crystalline surfaces were calculated. The effect of hydrogen substitution was studied.