Simple chemical solution deposition and thermoelectric properties of epitaxial La0.95Sr0.05CoO3 thin films

In this paper, simple chemical solution deposition method is used to prepare La_0.95Sr_0.05CoO₃ thin films on SrTiO₃ (001) substrates by acetate-based precursors. The derived film is characterized by x-ray diffraction, field-emission scanning electron microscopy and transmission electronic microscopy. The derived film is epitaxial growth with < 001>[100] La_0.95Sr_0.05CoO₃||<001>[100] SrTiO₃, indicating that the chemical solution deposition is an effective route to obtain the cobalt-based films. The resistivity, Seebeck coefficient and thermal power factor are 0.05Ω cm, 250 μV/K and 0.21 mWK^− 2m^− 1 at 300 K, respectively, which is higher than these of the ceramics, indicating epitaxial thin film is an effective route to enhance the thermoelectric properties of La_0.95Sr_0.05CoO₃.     

Thickness dependent microstructural changes in La0.5Ca0.5MnO3 thin films deposited on (111) SrTiO3

The epitaxial strain can modify the physical properties of complex oxide thin films considerably. The strain effect is expected to be less pronounced for relatively thick films and the physical properties should resemble to the bulk material. However, it has been recently observed that the electronic and magnetic properties of La_0.5Ca_0.5MnO₃ thin films deposited on (111) SrTiO₃ substrates thicker than a threshold value differ considerably from the bulk material. This observation is a hint for some interesting microstructural features in these films. In the present study, the microstructure of La_0.5Ca_0.5MnO₃ thin films on (111) SrTiO₃ substrates is investigated by X-ray diffraction and high resolution transmission electron microscopy.     

Growth of SrTiO3 thin epitaxial films by aerosol MOCVD

SrTiO₃ thin films were prepared by aerosol metal-organic chemical vapour deposition on (001) MgO, R-plane Al₂O₃ and (001) Si single-crystal substrates. Strontium tetramethyl heptadionate and titanium n-butoxide dissolved in diethyleneglycol dimethyl ether were used as precursors. The structure of the films was investigated by X-ray diffraction and transmission electron microscopy. Epitaxial films with [001] and [111] orientation perpendicular to the substrate surface were obtained on MgO and Al₂O₃, respectively. The epitaxial films on the MgO substrate were found to be in a relaxed state with lattice parameters corresponding to the bulk values. SrTiO₃ films on the Si substrate were grown as highly textured in the [011]direction and randomly oriented in the plane parrallel to the substrate surface.     

The demonstration of epitaxial and electronic-magnetic properties for La0.67Sr0.33MnO3−δ films with (1 1 1) orientation

La_0.67Sr_0.33MnO_3−δ films, fabricated on (1 1 1) LaAlO₃ single-crystal substrates using a direct current magnetron sputtering technique, are demonstrated by X-ray diffraction patterns and pole figures to be high quality epitaxial films and there is a perfect matching relationship between the films and the substrates. We observed an obvious difference of the electronic-magnetic transportation properties among films sputtered on (1 1 1), (1 0 0) and (1 1 0) LaAlO₃ substrates, respectively. A mechanism for the difference is discussed briefly.     

Strain effects and phase separation tendency in highly strained La0.7Ba0.3MnO3 thin films on LaAlO3 substrates

The magnetic and transport properties of epitaxial La_0.7Ba_0.3MnO₃ films on LaAlO₃ substrates have been investigated and compared with those on SrTiO₃ substrates. It is found that the ferromagnetic and metallic transition temperature of the highly compressive strained films on LaAlO₃ substrates decreases steadily with decreasing film thickness, while it changes little in the lightly strained films on SrTiO₃ substrates. The properties of the films on LaAlO₃ substrates are more sensitive to a post-annealing procedure. A tendency to phase separation, which induces a difference between the insulator-metal transition temperature T_MI and the Curie temperature T_C, is observed for the films with a medium oxygen annealing process. We argue that the phase separation is due to both the highly compressive strain and oxygen deficiency in the films.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.     

Dielectric and structural characterization of KNbO3 ferroelectric thin films epitaxially grown by pulsed laser deposition on Nb doped SrTiO3

KNbO₃ thin films were deposited on SrTiO₃ substrates by pulsed laser deposition. The X-ray diffraction patterns highlight an epitaxial growth according to the (011) orientation. This epitaxial growth was then confirmed by Electron Channeling Pattern. In agreement with the structural characteristics the dense microstructure consists in regular and ordered grains. Dielectric measurements were performed in the 20 Hz to 1 MHz frequency range on a KNbO₃ thin film grown on 2 at.% Nb doped (100)SrTiO₃ substrate in a large range of temperature in order to investigate the paraelectric-ferroelectric transition. Measurements at room temperature revealed a dielectric constant of 450 at 10 kHz and a minimum value of the loss tangent of 0.075 at 100 kHz. Dielectric study in the 20-600 °C temperature range showed a maximum of permittivity at the Curie temperature T_c = 410 °C and evidenced a “progressive” first-order phase transition, different from the classical “diffuse” transition.     

Improved dielectric properties of chemical solution derived Pb0.5Sr0.5TiO3 thin films by a layer-by-layer annealing method

Pb_0.5Sr_0.5TiO₃ thin films were prepared on Pt/TiO₂/SiO₂/Si and LaNiO₃ (LNO)/Si substrates by using chemical solution deposition technique, and a layer-by-layer annealing method was used in an attempt to improve the dielectric properties of the thin films. The structure, dielectric, and ferroelectric properties of the thin films were investigated. Improved dielectric properties of the thin films were clearly confirmed: the dielectric constant and dielectric loss for the films on Pt/TiO₂/SiO₂/Si substrates annealed at 650 °C were 1064 and 0.027, respectively, at 1 kHz, with a dielectric tunability of more than 50%; similarly, the films prepared on LNO/Si substrates, showed a high dielectric constant of 1280 and a low dielectric loss of 0.023, at 1 kHz. P-E hysteresis loop measurements indicated that the remanent polarization and coercive field for the films on Pt/TiO₂/SiO₂/Si substrates annealed at 650 °C were 15.7 μC/cm² and 51 kV/cm, respectively.     

Twinning of YBa2Cu3O7 thin films on different substrates

The twinning of YBa₂Cu₃O₇ (YBCO) thin films with c-axis orientation on (001) MgO, (001) SrTiO₃, (012) LaAlO₃, (110) NdGaO₃ and (001) NdGaO₃ substrates, prepared by laser ablation, has been examined using a combination of and θ/2θ scans at a four-circle diffractometer. On all substrates, except for (001) NdGaO₃, the tetragonal to orthorhombal phase transition results in four different orientations of YBCO twins relating to the substrate. On (001) NdGaO₃ only two different twin orientations, accompanied by a slight lattice monoclinization, has been observed.     

Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

Precursor chemistry for the solution deposition of epitaxial La0.66Sr0.33MnO3 (LSMO) thin films

A new chemical solution deposition method for the epitaxial growth of La_0.66Sr_0.33MnO₃ (LSMO) thin films from metal acetates, acetylacetonates and propionic acid is presented. Using this method, epitaxial LSMO thin films were grown on (001) SrTiO3 (STO) single crystalline substrates in the temperature range from 800 °C to 1100 °C, both in air and in oxygen atmosphere. The LSMO thin films exhibit good structural and electrical properties. The FWHM of the ω-scan for the (002) peak has a mean value of 0.06°. The Curie temperature of the LSMO thin films is about 320 K and 350 K for the annealed in oxygen and air, respectively.     

Structural engineering of Ba0.5Sr0.5TiO3 epitaxial films

Ba_0.5Sr_0.5TiO₃ single-layered and multilayered films were epitaxially grown on a (001) LaAlO₃ substrate using single target and dual target pulsed laser deposition, respectively. Compared to the single-layered films, the multilayered films exhibited broader phase transition and improved thermo-stability. The microstructure of these epitaxial films was investigated using high-resolution transmission electron microscopy in details. Misfit and threading dislocations were observed in the single-layered film, while the threading dislocations were dramatically decreased and no misfit dislocations were found in the multilayered film. It is suspected that the difference in dislocation densities is responsible for the different behaviors of the permittivity with temperature.     

Self-patterned Nano Structures in Structurally Gradient Epitaxial La0.5Ba0.5CoO3 Films

Highly epitaxial La_0.5Ba_0.5CoO₃ (LBCO) thin films with sharp interface and a thickness of 200 nm were epitaxially grown on (001) SrTiO₃ substrates using pulsed laser deposition. High-resolution transmission electron microscopy and electron diffraction analysis revealed that the films have a triple-layered structure. The first layer, close to the film/substrate interface, has a thickness of ~ 6 nm and is a defect free single crystal disordered cubic structure (a = 3.882 Å) which has a lattice mismatch of − 0.59% with respect to the substrate. The second layer which dominates the film structure has a single crystal disordered cubic structure (a = 3.854 Å) which has a lattice mismatch of − 1.31% with respect to the substrate. The third layer located on the top of the film has a thickness of several nanometers and consists of 112-type ordered tetragonal structure. The cubic structures in the first and second layer have an orientation relationship of (001)_LBCO//(001)_STO and < 100 > _LBCO//< 100 > _STO with respect to the substrate. Self-patterned 3-dimensional nano structures with a dimension range from 2 to 10 nm were formed in the second and third layers. These nano structures were formed by the enclosure of anti-phase boundary planes which are parallel to the {100} of the cubic structure. Epitaxial LBCO thin films with such nano structures are hard ferromagnetic with a large coercive field value and magnetoresistance effect value (~ 24%), and exhibit semiconductor behavior at temperatures < 300 K.     

Preparation, magnetic and microwave absorption properties of La0.5Sr0.5MnO3/La(OH)3 composites

La_0.5Sr_0.5MnO₃/La(OH)₃ composites with different weight ratio of La_0.5Sr_0.5MnO₃ particles and La(OH)₃ nanowires have been prepared by tuning the reaction time under hydrothermal conditions. The structure, morphology and magnetic properties have been investigated. Additionally, by the measurements of the complex permittivity, permeability and microwave absorption properties in the frequency range of 1-12 GHz, the results shown that the weight ratio of La(OH)₃ nanowires has great influence on reflection loss. Excellent absorption property can be obtained when the ratio is 1.4%, which is attributed to the enhanced electromagnetic match as well as the proper dielectric loss and magnetic loss. The enhanced electromagnetic match is originated from the improved frequency dispersion of the complex permittivity and permeability due to the presence of dielectric La(OH)₃ nanowires.     

Growth and structure characterization of epitaxial Bi2Sr2Co2Oy thermoelectric thin films on LaAlO3 (001)

Epitaxial Bi₂Sr₂Co₂O_y thin films with excellent c-axis and ab-plane alignments have been grown on (001) LaAlO₃ substrates by chemical solution deposition using metal acetates as starting materials. Microstructure studies show that the resulting Bi₂Sr₂Co₂O_y films have a well-ordered layer structure with a flat and clear interface with the substrate. Scanning electron microscopy of the films reveals a step-terrace surface structure without any microcracks and pores. At room temperature, the epitaxial Bi₂Sr₂Co₂O_y films exhibit a resistivity of about 2 mΩ cm and a seebeck coefficient of about 115 μV/K comparable to those of single crystals.     

Large-distance rf- and dc-sputtering of epitaxial La1 − xSrxMnO3 thin films

Studies on large-distance sputtering as an effective alternative to molecular beam epitaxy, pulsed laser deposition or off-axis sputtering for the deposition of epitaxial La_1 − xSr_xMnO₃ (LSMO) thin films, are reported. The focus of this study is on the quality of the samples and their structural and magnetic properties. The dependence of the characteristics of the LSMO films on the sputtering mode (rf, dc) and the sputtering parameters, in particular on the oxygen partial pressure is established and discussed. It is shown that large-distance sputtering can provide high quality LSMO thin films without the need for post-annealing.     

Growth of epitaxial YSZ films on LiNbO3 substrates

We report on the epitaxial growth and characterization of yttria-stabilized zirconia (YSZ) films on X-cut LiNbO₃ single crystals. Epitaxial (100) YSZ films were synthesized by the on-axis RF magnetron sputtering technique. Extensive analyses of the structure and microstructure of films with different thickness reveals the existence of an Li-deficient phase, LiNb₃O₈, at the interface between the substrate and the film. The origin of the presence of this interface is discussed, as well as its consequences on the structural and morphologic properties of the epitaxial YSZ film.     

Orientation control of epitaxial Ge thin films growth on SrTiO3 (100) by ultrahigh vacuum sputtering

We report the orientation control of crystalline Ge (111) and Ge (001) growth on SrTiO₃ (100) substrate by adjusting the temperature of substrate. It is found that the substrate temperature plays an important role for the formation of crystalline Ge with different surface orientations and interfacial chemical configuration during the sputtering process. At 500 °C, Ge (111) with good crystalline quality is formed, while Ge (001) is preferably grown on SrTiO₃ substrate at 650 °C. Our results show the possibility of manipulating the surface orientations during Ge growth on SrTiO₃ by controlling the substrate temperatures.     

Dislocations in Bi0.4Ca0.6MnO3 epitaxial film grown on (110) SrTiO3 substrate

Bi_0.4Ca_0.6MnO₃ (BCMO) film with a thickness of 110 nm was epitaxially grown on a (110) SrTiO₃ (STO) substrate using pulsed laser ablation technique. The microstructure of the epitaxial films was investigated by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) in details. Two different kinds of dislocations, one being perpendicular to the BCMO/STO interface, the other being parallel to the interface, have been commonly observed. The formation mechanism for these dislocations has been discussed. All the dislocations are thought to relieve the local strain in the epitaxial film.     

Ferroelectric and pyroelectric properties of (Na0.5Bi0.5)TiO3-BaTiO3 based trilayered thin films

Trilayered Bi_3.25La_0.75Ti₃O₁₂ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Bi_3.25La_0.75Ti₃O₁₂ (25 nm) and Pb(Zr_0.4Ti_0.6)O₃ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Pb(Zr_0.4Ti_0.6)O₃ (25 nm) thin films without undesirable phases have been deposited on Pt/Ti/SiO₂/Si substrates. It was found that the Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃ layers are very effective to inhibit the charge transport in the trilayered films. Much better insulating properties than those of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ films have been achieved in the trilayered films. The trilayered films show good dielectric, ferroelectric and pyroelectric properties. Remnant polarizations 2P_r of 16 µC/cm² and 34 µC/cm², pyroelectric coefficients of 4.8 × 10^− 4 C m^− 2 K^− 1 and 7.0 × 10^− 4 C m^− 2 K^− 1 have been obtained for the Bi_3.25La_0.75Ti₃O₁₂/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Pb(Zr_0.4Ti_0.6)O₃ thin films, respectively. The trilayered films are promising candidates for sensor and actuator applications.