Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

Finite element analysis of postbuckling and delamination of composite laminates using virtual crack closure technique

The two-dimensional and three-dimensional parametric finite element analysis (FEA) of composite flat laminates with two through-the-width delamination types: 0₄/(±θ)₆//0₄ and 0₄//(±θ)₆//0₄ (θ = 0°, 45°, and “//” denotes the delaminated interface) under compressive load are performed to explore the effects of multiple delaminations on the postbuckling properties. The virtual crack closure technique which is employed to calculate the energy release rate (ERR) for crack propagation is used to deal with the delamination growth. Three typical failure criteria: B-K law, Reeder law and Power law are comparatively studied for predicting the crack propagation. Effects of different mesh sizes and pre-existing crack length on the delamination growth and postbuckling properties of composite laminates are discussed. Interaction between the delamination growth mechanisms for multiple cracks for 0₄//(±θ)₆//0₄ composite laminates is also investigated. Numerical results using FEA are also compared with those by existing models and experiments.     

Synthesis of epitaxial BaZrO3 thin films by chemical solution deposition

This work reports on the low temperature preparation and characterization of BaZrO₃ (BZO) epitaxial thin films by chemical solution deposition (CSD). The X-ray θ-2θ scan and φ-scan measurements have demonstrated that the BZO films exhibit cube-on-cube epitaxy on (100) MgO substrates, with the full width at half maximum (FWHM) for the ω-scan and φ-scan of 0.35° and 0.46°, respectively. The SEM and AFM analyses revealed that the morphology of the films is strongly correlated with annealing temperature. The root mean square roughness for the film annealed at 600 °C is 3.63 nm, while for the film grown at 1000 °C is 5.25 nm.     

Conductivity and adhesion enhancement in low-temperature processed indium tin oxide/polymer nanocomposites

We report on the conductivity and adhesion enhancement of indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films by the application of polymers as matrix material. We fabricated ITO layers at a maximum process temperature of 130 °C by modifying and spin-coating nanoparticulate ITO dispersions. Dispersions containing the organic film-forming agent polyvinylpyrrolidone (PVP) and the organofunctional coupling agent 3-methacryloxypropyltrimethoxysilane (MPTS) have been developed to obtain transparent and conducting coatings on substrates which do not withstand high process temperatures like polymers or already processed glasses. The layers were cured by UV-irradiation as well as by low-temperature heat treatment (T = 130 °C) in air and under forming gas atmosphere (N₂/H₂). The influence of the additives on the electrical, optical, morphological and mechanical layer properties is reported. Compared to best pure ITO layers (3.1 Ω^− 1 cm^− 1), the ITO-MPTS-PVP nanocomposite coatings exhibit a conductance of 9.8 Ω^− 1 cm^− 1. Stable sheet resistances of 750 Ω/□ at a coexistent transmittance of 86% at 550 nm for a layer thickness of about 1.3 µm were achieved. The conductance enhancement is a consequence of the consolidation of the ITO nanoparticle network due to the acting shrinkage forces caused either by drying in the case of PVP or UV-irradiation induced condensation and polymerization reactions in the case of MPTS.     

Structure and magnetic properties of Fe epitaxial thin films prepared by UHV rf magnetron sputtering on GaAs single-crystal substrates

Fe thin films were prepared on GaAs single-crystal substrates of (100)_B3, (110)_B3, and (111)_B3 orientations by ultra high vacuum rf magnetron sputtering. The effects of substrate orientation and substrate temperature on the film growth, the structure, and the magnetic properties were investigated. On GaAs(100)_B3 substrates, Fe(100)_bcc single-crystal films are obtained at 300 °C, whereas Fe films consisting of bcc(100) and bcc(221) crystals epitaxially grow at room temperature (RT). Fe(110)_bcc and Fe(111)_bcc single-crystal films are respectively obtained on GaAs(110)_B3 and GaAs(111)_B3 substrates at RT-300 °C. The in-plane lattice spacings of these Fe epitaxial films are 0-9% larger than the out-of-plane lattice spacings due to accommodation of lattice mismatch between the films and the substrates. The film strain is decreased by employing an elevated substrate temperature of 300 °C. The in-plane magnetization properties are reflecting the magnetocrystalline anisotropy of bulk bcc-Fe crystal.     

Growth of silicon carbide nanorods from the hybrid of lignin and polysiloxane using sol-gel process and polymer blend technique

We report here the formation of silicon carbide (SiC) nanorods from organic-inorganic hybrid of the commercially available lignin and sol-gel derived nanosized silica. The SiC nanorods were identified by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface morphology shows the formation of continuous nanorods of diameter in the range of 50-200 nm. The X-ray diffraction (XRD) pattern show peaks at 2θ = 35.5° and 60.2° indicate the formation of β-SiC and a sharp peak at 2θ = 22.1° suggests the presence of unreacted crystalline silica (crystoballite). The characteristic vibration of SiC at 791 cm^− 1 in Fourier transform infrared spectroscopy (FTIR) was also observed.     

Epitaxial orientation and morphology of β-FeSi2 produced on a flat and a patterned Si(001) substrates

The epitaxial growth of β-FeSi₂ films produced on flat and patterned Si(001) substrates under various substrate temperatures (T_s) with deposition rates of Fe (V_Fe) was investigated by transmission electron microscopy (TEM). In the film deposited on the flat Si(001) substrate, precipitates of flat-bottom shaped β-FeSi₂ and those of round-bottom shaped α-FeSi₂ were formed at T_s = 500 °C and V_Fe = 0.02 nm/s. The β-FeSi₂ adopted the epitaxy to (001)_Si plane, while α-FeSi₂ selected the epitaxy to {111}_Si planes inside the Si matrix. At T_s = 350 °C and V_Fe = 0.01 nm/s, a continuous β-FeSi₂ layer were formed epitaxially on the Si(001) substrate without forming α-FeSi₂. It was found that the lower temperature and the higher Fe-concentration suppress the formation of α-FeSi₂ and promote the formation of β-FeSi₂. In addition, the morphology of β-FeSi₂ changed from fine isolated precipitates (islands) to a continuous layer with increasing the deposition rate and the substrate temperature. In the film deposited on the patterned Si(001) substrate at T_s = 500 °C and V_Fe = 0.02 nm/s, on the other hand, both β- and α-FeSi₂ precipitates were formed on the top-hills and the valleys of the patterned substrate, while only α-FeSi₂ precipitates were formed on the sidewalls. These results demonstrate that not only the growth conditions but also geometric situations affect strongly the epitaxial growth of FeSi₂ precipitates.     

Epitaxial film growth of chromium dioxide by low pressure chemical vapor deposition using chromium carbonyl

Epitaxial chromium dioxide (CrO₂) thin films have been deposited by low pressure chemical vapor deposition (LPCVD) on (100) TiO₂ substrates using the precursor chromium hexacarbonyl (Cr(CO)₆) within a narrow temperature window of 380-400 °C. Normal θ-2θ Bragg x-ray diffraction results show that the predominant phase is CrO₂ with only a small amount of Cr₂O₃ present, mostly at the film surface. The LPCVD films have a reasonably smooth surface morphology with a root mean square roughness of 4 nm on a scale of 5 μm. Raman spectroscopy confirms the existence of rutile CrO₂ in the deposited films, while transmission electron microscopy confirms the single-crystalline nature of the films. The LPCVD films showing a dominant CrO₂ phase exhibit clear uniaxial magnetic anisotropy with the easy axis oriented along the c direction.     

Phase stabilization and microstructural studies of lead lanthanum titanate thin films

Thin ferroelectric films of PLTx (Pb_1−xLa_xTi_1−x/4O₃) have been prepared by a sol-gel spin coating process. As deposited films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various concentrations of La (x = 0.04, 0.08 and 0.12) on ITO coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out on films annealed at temperatures (350, 450, 550 and 650 °C). Characterization of these films by X-ray diffraction shows that the films annealed at 650 °C exhibit tetragonal phase with perovskite structure. Atomic force microscope (AFM) images are characterized by slight surface roughness with a uniform crack free, densely packed structure. Fourier transform infrared spectra (FTIR) studies of PLTx thin films (x = 0.08) deposited on Si substrates have been carried out to get more information about the phase stabilization.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Characterization of tetragonal BaTiO3 nanopowders prepared with a new soft chemistry route

Preparation of BaTiO₃ nanopowders (37-42 nm) is carried out by a controlled reconstructive thermal decomposition and crystallization from an amorphous polymeric precursor with polyvinyl alcohol (PVA) and sucrose at 400-600 °C in air. The Rietveld refinement of the XRD profile, processed at 600 °C in 2 h, infers the P4mm tetragonal crystal structure (95% of tetragonality) of the as prepared BaTiO₃ nanopowders, with a = 0.3994 nm and c = 0.4024 nm. A cubic symmetry (Pm3m) of 5% in amount with a = 4.0057 is also detected in addition with tetragonal symmetry. The characteristic tetragonal splitting of 002/200 XRD peaks also supports the tetragonal symmetry (c / a = 1.0075) of the as prepared BaTiO₃ nanopowders. The average particle size (D) of the BaTiO₃ powders, estimated with the help of the specific surface area, measured by BET method, is 39.91 nm. Average D value, calculated by Δ2θ_1 / 2 in the XRD peaks with the Debye Scherrer relation is ∼ 40 nm. TEM study measures the particle size of the BaTiO₃ powders with an average diameter of 37 to 42 nm.     

Effect of deposition angle on the structure and properties of pulsed-DC magnetron sputtered TiAlN thin films

This article reports the comparison of structure and properties of titanium aluminum nitride (TiAlN) films deposited onto Si(100) substrates under normal and oblique angle depositions using pulsed-DC magnetron sputtering. The substrate temperature was set at room temperature, 400 °C and 650 °C, and the bias was kept at 0, − 25, − 50, and − 80 V for both deposition angles. The surface and cross-section of the films were observed by scanning electron microscopy. It was found that as the deposition temperature increases, films deposited under normal incidence exhibit distinct faceted crystallites, whereas oblique angle deposited (OAD) films develop a kind of “tiles of a roof” or “stepwise structure”, with no facetted crystallites. The OAD films showed an inclined columnar structure, with columns tilting in the direction of the incident flux. As the substrate temperature was increased, the tilting of columns nearly approached the substrate normal. Both hardness and Young's modulus decreases when the flux angle was changed from α = 0° to 45° as measured by nanoindentation. This was attributed to the voids formed due to the shadowing effect. The crystallographic properties of these coatings were studied by θ-2θ scan and pole figure X-ray diffraction. Films deposited at α = 0° showed a mixed (111) and (200) out-of-plane orientation with random in-plane alignment. On the other hand, films deposited at α = 45° revealed an inclined texture with (111) orientation moving towards the incident flux direction and the (200) orientation approaching the substrate normal, showing substantial in-plane alignment.     

Structural, optical, and electrical properties of AZO films by tilted angle sputtering method

We investigate the structural, optical, and electrical properties of aluminum-doped zinc oxide (AZO) films on Si substrate by a tilted angle sputtering method. The substrate holder is tilted by varying the angle from θ_sh = 0° to θ_sh = 80° during the sputtering process. As the tilted angle is increased, the deposition rate is increased due to the decreased distance between the substrate and the target. Without substrate rotation, the deposited AZO films exhibit apparently the inclined nanocolumnar structures, depending on the tilted angle. The refractive index, which is related to the porosity within films, is reduced for the larger inclined nanocolumnar structure while the extinction coefficient remains almost the same in the visible wavelength range. The inclination of nanocolumns disappears when the substrate is rotated. On glass substrate, the electrical properties as well as optical transmittance of AZO films are also dependant on the tilted angle.     

Modification of AZO thin-film properties by annealing and ion etching

Effects of annealing and ion etching on the structural, electrical and optical properties of sputtered ZnO:Al (AZO) thin films were investigated. The post-deposition annealing at temperatures T_A = 200-400 °C in the forming gas (80% N₂/20% H₂) for 1 h and ion RF-sputter etching after annealing were used. Ion-sputter etching rate was 7 nm/min. The surface topography changed noticeably after ion-sputter etching: the surface of the sample was rougher (R_a = 33 nm) in comparison with annealed sample only (R_a = 9 nm). After the post-deposition annealing temperature T_A = 400 °C and ion-sputter etching thin films have higher integral transmittance (in the range of λ = 400-1000 nm) than non-etched samples. The figure of merit (F) became higher with increase of annealing temperature and the maximum value was F = 8%/Ω at T_A = 400 °C (R_s = 10 Ω, T_int = 86%).     

Low temperature (~ 250 °C) layer exchange crystallization of Si1 − xGex (x = 1-0) on insulator for advanced flexible devices

Low-temperature (~ 250 °C) layer exchange crystallization of poly-Si_1 − xGe_x (x = 1-0) films on insulators has been investigated for realization of advanced flexible devices. We propose utilization of Au as catalyst to enhance the crystallization at low temperatures. By annealing (~ 250 °C, 20 h) of the a-Si_1 − xGe_x (x = 1-0)/Au stacked structures formed on insulating substrates, the SiGe and Au layers exchange their positions, and Au/poly-SiGe stacked structures are obtained. The Ge fractions of the obtained poly-SiGe layers are identical to that of the initial a-SiGe layers, and there is no Si or Ge segregation. This low temperature crystallization technique enables poly-SiGe films on plastic substrates, which are essential to realize advanced flexible devices.     

紫外光引发低密度聚乙烯接枝聚N-异丙基丙烯酰胺的温敏改性

以二苯甲酮(BP)为光敏剂,采用两步表面光接枝法将N-异丙基丙烯酰胺(NIPAAm)单体接枝到低密度聚乙烯(LDPE)表面,赋予LDPE表面温敏性。通过红外光谱和扫描电子显微镜等对LDPE-g-PNIPAAm的结构进行了表征;采用调制差示扫描量热分析技术和表面水接触角测定法研究了LDPE-g-PNIPAAm的温敏性;讨论了引发剂浓度、光还原时间、单体浓度和光照时间对接枝率的影响。结果表明,LDPE-g-PNIPAAm具有温敏亲/疏水性,其低临界溶解温度(LCST)在33℃左右。增加引发剂浓度、单体浓度、延长光还原时间和光照时间都能使接枝率增加;且可以通过调节这4种因素来控制接枝率。     

Three-dimensional stress state around quarter-elliptical corner cracks in elastic plates subjected to uniform tension loading

Detailed full-field three-dimensional (3D) finite element analyses have been conducted to study the out-of-plane stress constraint factor T_z around a quarter-elliptical corner crack embedded in an isotropic elastic plate subjected to uniform tension loading. The distributions of T_z are studied in the forward section (0° ? θ ? 90°) of the corner cracks with aspect ratios a/c of 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0. In the normal plane of the crack front line, T_z drops radially from Poisson’s ratio at the crack tip to zero beyond certain radial distances. Strong 3D zones (T_z > 0) exist within a radial distance r/a of about 4.6-0.7 for a/c = 0.2-1.0 along the crack front, despite the stress-free boundary conditions far away. At the same radial distance along the crack front in the 3D zones, T_z increases from zero on one free surface to a peak value in the interior, and then decreases to zero on another free surface. The distributions of T_z near the corner points are also discussed. Empirical formulae describing the 3D distributions of T_z are obtained by fitting the numerical results, which prevail with a sufficient accuracy in the valid range of 0.2 ? a/c ? 1.0 and 0° ? θ ? 90° except very near the free surfaces where T_z is extremely low. Combined with the K-T solution, the transition of approximate plane-stress state near the surfaces to plane-strain state in the interior can be characterized more accurately.     

Magneto-optical Kerr-effect studies on copper oxide thin films produced by atomic layer deposition on SiO2

This work demonstrates the sensitivity of magneto-optical Kerr-effect (MOKE) spectroscopy to ultra-thin nonmagnetic films using the example of copper oxide. The films with an effective thickness between 0.6 nm and 6 nm are produced by atomic layer deposition (ALD) on silicon oxide substrates based on the Cu(I) β-diketonate precursor [(ⁿBu₃P)₂Cu(acac)] (acac = acetylacetonate) at a process temperature of 120 °C. The copper oxide films exhibit magneto-optical activity in the spectral ranges around 2.6 eV and above 4 eV. The evolution of the spectral features as a function of the number of ALD cycles is simulated numerically using the dielectric function and the Voigt constant of Cu₂O as input parameters. The comparison between experimental and simulated MOKE spectra strengthens the conclusion drawn from spectroscopic ellipsometry studies that the thin film optical constants differ markedly from the bulk ones.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.     

Growth of epitaxial Cu on MgO(001) by magnetron sputter deposition

100-nm-thick Cu layers were grown on MgO(001) substrates by ultra-high vacuum magnetron sputter deposition at substrate temperatures T_s ranging from 40 to 300 °C. X-ray diffraction ω−2θ scans, ω-rocking curves, and pole figures show that layers grown at T_s = 40 and 100 °C are complete single crystals with a cube-on-cube epitaxial relationship with the substrate: (001)_Cu||(001)_MgO with [100]_Cu||[100]_MgO. In contrast, T_s ≥ 200 °C leads to polycrystalline Cu layers with 001, 203, and 1¯75-oriented grains. The transition from a single- to a polycrystalline microstructure with increasing T_s is attributed to temperature-induced mass transport that allows Cu nuclei to sample a larger orientational space and find lower energy (and/or lower lattice mismatch) configurations. The large Cu- to-MgO lattice mismatch of 14% is relieved by 7 × 7 Cu unit cells occupying 6 × 6 MgO cells. In addition, for T_s ≥ 200 °C, the 001-oriented grains relax by tilting by 4° or 15° about 〈110〉 or 〈100〉 axes, respectively, while the 203 and 1¯75-oriented grains exhibit complex epitaxial relationships with the substrate: (203)_Cu||(001)_MgO with [010]_Cu||[110]_MgO and [302¯]_Cu||[11¯0]_MgO; and (1¯75)_Cu||(001)_MgO with [211¯]_Cu||[100]_MgO and [43¯5]_Cu||[010]_MgO. The surface roughness, as determined by X-ray reflectivity, increases with growth temperature. The smoothest layers are grown at 40 °C and exhibit an rms surface and buried interface roughness of 0.7 and 1.4 nm, respectively.