X-ray photoelectron diffraction study of ultrathin PbTiO3 films

Full hemispherical X-ray photoelectron diffraction (XPD) experiments have been performed to investigate at the atomic level ultrathin epitaxial c-axis oriented PbTiO₃ (PTO) films grown on Nb-doped SrTiO₃ substrates. Comparison between experiment and theory allows us to identify a preferential ferroelectric polarization state in a 60 ? -thick PTO film. Multiple scattering theory based on a cluster-model [ Phys. Rev. B , 075404 (2001)] is used to simulate the experiments.     

Thickness-dependent surface morphology of La0.9Sr0.1MnO3 ultrathin films

La_0.9Sr_0.1MnO₃ (LSMO) ultrathin films with various thickness (in the range of 5-50 unit cells) are grown on (0 0 1) substrates of the single-crystal SrTi_0.99Nb_0.01O₃ by laser molecular-beam epitaxy (laser-MBE), and the surface morphology of these films were measured by scanning tunneling microscopy (STM). STM images of LSMO ultrathin film surface reveal that surface morphology becomes more flat with increasing film thickness. This study highlights the important effect of strain caused by the lattice mismatch between substrates and ultrathin films. And the results should be useful to the investigations on growing manganite perovskite materials.     

Structure and electronic properties calculation of ultrathin α-Al2O3 films on (0 0 0 1) α-Cr2O3 templates

Ab initio total energy Hartree-Fock calculations of ultrathin films of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates are presented. The surface relaxation, the in-plane reconstruction and the surface and strain energies of the slabs are studied as a function of alumina film thickness. The surface Al layer is found to relax inwards considerably, with the magnitude of the inwards relaxation depending on the thickness of the ultrathin alumina film in a non-linear manner. The calculations also reveal that ultrathin films of alumina lower the surface energy of (0 0 0 1) α-chromia substrates. This indicates that the (0 0 0 1) α-chromia surface provides favourable conditions for the templated growth of α-alumina. However, increasing the alumina film thickness is found to give rise to a significant increase in strain energy. Finally, the electronic properties at the surface of the (0 0 0 1) α-Al₂O₃/α-Cr₂O₃ slabs are investigated. Here it is found that the alumina coating gives rise to an increase in the covalency of the bonds at the surface of the slabs. In contrast, the influence of an alumina layer on the electrostatic potential at the surface of the chromia slab is relatively minor, which should also be beneficial for the templated growth of α-alumina on (0 0 0 1) α-chromia substrates.     

Control of tensile stress on inducing formation and tunability of (100) oriented Pb x Sr1−x TiO3 thin films

(100) Oriented Pb _x Sr_1?x TiO₃ (PSTO) thin films are prepared on indium tin oxide (ITO)/glass substrates by sol–gel technique while inserting doped PbTiO₃ (PTO)-inducing layer in between. The effect of tensile stress in PSTO on tunability and (100) orientation of the thin films was investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscope, and atomic force microscope, respectively. Results show that PSTO thin film deposited on doped PTO has (100) oriented structure while it is randomly oriented when deposited directly on the ITO/glass substrate. Lattice mismatch between PSTO and PTO appears, in which the in-plane lattice constant c is 0.3922–0.3924 nm in the former and 4.02–4.07 nm in the latter, respectively, contributing tensile stress in the PSTO due to different lattice constants between them. The stress in the PSTO thin film is 3.04, 3.15, 3.59 and 4.47 GPa when the doped PTOs are Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively. The orientation degrees of PSTO thin films are from 89.63, 90.31, 91.92 to 93.29 % with increasing stress of PSTO on Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively. Tunabilities of the well-oriented PSTO thin films increase in ascending order of 63 < 65 < 69 < 73 % when induced by oriented PTO layers of Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively, which is in accordance with the degree of (100) orientation appearing in the thin films. The high tunability appears in the PSTO thin film while high (100) orientation is derived from the tensile stress. It is much higher than that of randomly oriented PSTO thin film.     

Particle-free superconducting Bi2Sr2CaCu2Ox ultrathin films prepared by atomic-layer-controlled molecular beam epitaxy technique

Atomic-layer-controlled molecular beam epitaxy (ALC-MBE) technique is applied for preparing Bi₂Sr₂CaCu₂O_x ultrathin films. Precise control of the composition by ALC-MBE enables successful growth of particle-free ultrathin films. Superconducting zero-resistance transitions are observed for the films more than 3.0 nm in thickness. It is also shown that growth of a Bi₂Sr₂CuO_y buffer layer between the film and SrTiO₃(100) substrate contributes to preparing such particle-free ultrathin films with good superconducting properties.     

Optical investigation of the metal-insulator transition in the manganite films with the thickness dependence

We investigated the optical response of La_0.67Sr_0.33MnO₃ (LSMO) films which show the metal-insulator transition (MIT) with the film thickness dependence. By using spectroscopic ellipsometric technique we found that the optical spectra below the charge transfer gap exhibited the coherent-incoherent crossover behavior through MIT. The formation of the incoherent mode near 1.5 eV was reminiscent of the polaron absorption which had been widely observed in various manganites. We suggest that the electron-phonon coupling could be enhanced due to low dimensionality in the ultrathin LSMO film in consideration of orbital polarization.     

Effects of oxygen partial pressure on the ferroelectric properties of pulsed laser deposited Ba0.8Sr0.2TiO3 thin films

The Ba_0.8Sr_0.2TiO₃ thin films were grown on the Pt–Si substrate at 700 °C by using a pulsed laser deposition technique at different oxygen partial pressure (PO₂) in the range of 1–20 Pa and their properties were investigated. It is observed that the PO₂ during the deposition plays an important role on the tetragonal distortion ratio, surface morphology, dielectric permittivity, ferroelectric polarization, switching response, and leakage currents of the films. With an increase in PO₂, the in-plane strain for the BST films changes from tensile to compressive. The films grown at 7.5 Pa show the optimum dielectric and ferroelectric properties and also exhibit the good polarization stability. It is assumed that a reasonable compressive strain, increasing the ionic displacement, and thus promotes the in-plane polarization in the field direction, could improve the dielectric permittivity. The butterfly features of the capacitance–voltage (C–V) characteristics and the bell shape curve in polarization current were attributed to the domain reversal process. The effect of pulse amplitude on the polarization reversal behavior of the BST films grown at PO₂ of 7.5 Pa was studied. The peak value of the polarization current shows exponential dependence on the electric field.     

Substrate effect on mechanical relaxation of polystyrene in ultrathin films

Mechanical relaxation behavior in ultrathin polystyrene (PS) films supported on silicon oxide (SiO_x) and gold (Au) substrates has been studied by dynamic viscoelastic measurement. Based on the method, effects of free surface and substrate interface on the segmental dynamics were discussed. In the case of thin PS films with a thickness of approximately 200 nm, α_a-relaxation process corresponding to the segmental motion did not show any deviation from the bulk behavior. In contrast, for the films thinner than about 50 nm, the relaxation time distribution for the α_a-process became broader, probably due to a mobility gradient in the surface and interfacial regions. When we sandwiched an ultrathin PS film between SiO_x layers, another relaxation process, in addition to the original α_a-process, appeared at a higher temperature side that we assigned to the interfacial α_a-relaxation process. However, this was never seen for an ultrathin PS film between Au layers, implying that restriction from the substrate interface might be weak in this case.     

A first-principles study of phase transitions in ultrathin films of BaTiO3

We determine the effects of film thickness, epitaxial strain and the nature of electrodes on ferroelectric phase transitions in ultrathin films of BaTiO₃ using a first-principles effective Hamiltonian in classical molecular dynamics simulations. We present results for polarization and dielectric properties as a function of temperature and epitaxial strain, leading to size-dependent temperature-strain phase diagram for the films sandwiched between ‘perfect’ electrodes. In the presence of non-vanishing depolarization fields when non-ideal electrodes are used, we show that a stable stripe-domain phase is obtained at low temperatures. The electrostatic images in the presence of electrodes and their interaction with local dipoles in the film explain these observed phenomena.      

Size effect on SrRuO3/BaTiO3/SrRuO3 ferroelectric ultrathin film capacitor

We have carried out a detailed investigation on the size effect on SrRuO₃/BaTiO₃/SrRuO₃ ferroelectric ultrathin film capacitors with film thickness fully strained with a SrTiO₃ substrate. We employ the transverse field Ising model, taking into account the incomplete charge compensation of the realistic SrRuO₃ electrode and the misfit strain imposed by the SrTiO₃ substrate in the Hamiltonian, to quantitatively explain the experimental observation in the literature. It is found that BaTiO₃ ultrathin films between two metallic electrodes lose their ferroelectric properties below a critical thickness of about 4.17 nm due to the enhancement of the quantum effect under the influence of the incomplete charge compensation of the electrode.     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Thickness-dependence of optical constants for Ta2O5 ultrathin films

An effective method for determining the optical constants of Ta₂O₅ thin films deposited on crystal silicon (c-Si) using spectroscopic ellipsometry (SE) measurement with a two-film model (ambient–oxide–interlayer–substrate) was presented. Ta₂O₅ thin films with thickness range of 1–400 nm have been prepared by the electron beam evaporation (EBE) method. We find that the refractive indices of Ta₂O₅ ultrathin films less than 40 nm drop with the decreasing thickness, while the other ones are close to those of bulk Ta₂O₅. This phenomenon was due to the existence of an interfacial oxide region and the surface roughness of the film, which was confirmed by the measurement of atomic force microscopy (AFM). Optical properties of ultrathin film varying with the thickness are useful for the design and manufacture of nano-scaled thin-film devices.     

Spin-resolved photoelectron spectroscopy of the MgO/Fe(110) system

The surface structure and electronic properties of ultrathin MgO layers grown on epitaxial Fe(110) films were investigated at room temperature by means of electron diffraction, Auger electron spectroscopy, scanning tunneling microscopy, and spin-resolved photoelectron spectroscopy. The spin polarization at the Fermi level (E_F) of the Fe(110) film decreases sharply with increasing thickness of the MgO layer. This behavior arises from the formation of a thin FeO layer at the MgO(111)/Fe(110) interface, as revealed by structural and spectroscopic investigations. The strong attenuation of the intrinsic spin polarization is qualitatively attributed to the scattering of spin-polarized electrons at the unoccupied d-orbitals of Fe²⁺. PACS 68.35.-p; 68.55.-a; 73.20.r; 75.70.Cn; 79.60.-I     

Brillouin scattering from ultra thin iron films

The spin-wave excitations of ultrathin iron films (1 to 5 nm) on sapphire substrates have been studied by inelastic light scattering using Brillouin spectroscopy. The room temperature magnetization J, magnetic anisotropy field B_an, and the g-factor have been determined by fitting the measured ω-B results for surface spin waves to the related Damon-Eshbach theory. For thicknesses below 4 nm the film magnetization J_f decreases linearly with film thickness and is found substantially smaller than J_f values determined by static magnetization measurements. Equivalent reductions in J_f, however, were also obtained in light scattering studies of ultrathin Fe films on GaAs substrates reported previously in the literature [2].     

外延PbZr0.4Ti0.6O3薄膜厚度对其铁电性能的影响

从Landau-Devonshire唯象理论出发，考虑到晶格失配导致的NFDA3位错应力场与极化场的耦合，研究了在SrTiO₃衬底上外延生长的PbZr_0.4Ti_0.6O₃薄膜厚度对其自发极化强度、电滞回线的影响. 结果表明，产生刃位错的PbZr_0.4Ti_0.6O₃薄膜临界厚度为～1.27nm，当薄膜厚度大于临界厚度时，在所形成的位错附近，极化强度出现急剧变化，形成自发极化强度明显减弱的“死层”；随着薄膜厚度的减小，位错间距增大，“死层”厚度与薄膜总厚度之比增加. 由薄膜电滞回线的变化情况可知，其剩余极化强度随着薄膜厚度的减小而逐渐减小. 关键词： 铁电薄膜 自发极化强度 电滞回线 位错     

Modification of electronic properties during adsorption of conjugate organic molecules on the surface of polycrystalline SnO<Subscript>2</Subscript>

The modification of the electronic structure during adsorption of ultrathin copper phthalocyanine (CuPc) and 3, 4, 9, 10 perylene-tetracarboxylic-dianhydride (PTCDA) coatings on the surface of polycrystalline tin dioxide is traced. Auger electron spectroscopy is employed to find changes in the atomic composition of the surface. It is found with the help of low-energy electron total current spectroscopy using a testing beam of electrons with energies up to 30 eV that the total current spectra typical of organic films are formed when the thickness of the coating being deposited is 2–7 nm. The formation of an interface layer 1.5–2.0 nm in thickness is detected, in which the intensity of the structure of the total current spectra decreases and the effect of interaction of PTCDA molecules with the SnO₂ surface is manifested.     

Morphology and thermal stability of AlF3 thin films grown on Cu(100)

The growth of ultrathin epitaxial layers of aluminum fluoride on Cu(100) has been studied by a combination of surface science techniques. Deposition at room temperature results in step decoration followed by the formation of dendritic two-dimensional islands that coalesce to form porous films. Ultrathin layers (up to 2 monolayers in thickness) are morphologically unstable upon annealing; de-wetting takes place around 430 K with the formation of three-dimensional islands and leaving a large fraction of the Cu surface uncovered. Films several nanometers thick, on the contrary, are stable up to ca. 730 K where desorption in molecular form sets on. The effect of electron irradiation on the AlF₃ has also been characterized by different spectroscopic techniques; we find that even small quantities of stray electrons from rear electron beam heating can provoke significant decomposition of the aluminum fluoride, resulting in the release of molecular fluorine and the formation of deposits of metallic aluminum. These features make AlF₃ an interesting material for spintronic applications.     

Tailoring of the spectral–directional characteristics of rare-earth fluorescence by metal–dielectric planar structures

It is demonstrated that the spectrum, direction and polarization of rare-earth fluorescence can be tailored by embedding the impurity ions into a planar metal–dielectric structure (MDS). The latter was designed by spin coating a rare-earth-doped oxide film (TiO₂:Sm³⁺) onto a gold-covered glass substrate. For spectral–directional investigations of Sm³⁺ fluorescence, the MDS was attached to a semi-cylindrical prism and excited by UV light from the flat side. An angular scan revealed a strongly polarized and directional emission of Sm³⁺ from the convex side of the prism. The tuning of TiO₂ film thickness in the MDS allows a control of the polarization and direction of the emission bands. A theoretical modeling of the reflectivity of the MDS suggests that the observed angular resonances in the fluorescence emission are caused by its effective coupling with surface plasmons on the gold–dielectric interface or coupling with leaky modes in sufficiently thick dielectric films working as a waveguides.     

Growth,structure, and thermal stability of epitaxial BaTiO3 films on Pt(111)

The growth of epitaxial ultrathin BaTiO₃ films upon rf magnetron sputter deposition on a Pt(111) substrate has been studied by scanning tunnelling microscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. The BaTiO₃ films have been characterized from the initial stages of growth up to a film thickness of 4 unit cells. The deposited films develop a long-range order upon annealing at 1050 K in UHV. In the submonolayer regime a wetting layer is formed on Pt(111). Thicker films reveal a Stranski–Krastanov-like structure as observed with STM. By XPS a good agreement of the thin film stoichiometry with BaTiO₃ single crystal data is determined. Due to annealing at 1150 K BaTiO₃ forms large two-dimensional islands on the Pt(111) substrate. Different surface structures develop on the islands depending on the O₂ partial pressure during annealing.     

Effect of size quantization on the effective mass in ultrathin films ofn-Cd3As2

An attempt is made to investigate the effects of size quantization on the effective mass in ultrathin films ofn-Cd₃As₂. It is found that the effective mass at the Fermi level depends on the size quantum number due to the effect of crystal-field splitting, resulting in different effective masses at the Fermi level corresponding to different electric subbands. It is also observed that the different effective masses closely approach each other, for a given film thickness, with increasing electron concentration and, for a given electron concentration, with increasing film thickness.