Growth control of stoichiometry in LaMnO3 epitaxial thin films by pulsed laser deposition

We have studied structural, magnetic, and optical transport properties of LaMnO₃ (LMO) thin films grown on SrTiO₃. While the stoichiometric LMO is an insulating antiferromagnet, it tends to be a ferromagnetic insulator when grown as thin films. By exploring the majority of growth parameters, we have found that the bulk-like electronic and magnetic phases can be stabilized by growing thin films under reducing atmospheres and by using more energetic laser processes. These conditions are found to reduce the La deficiency in the film resulting in the greatly improved cation stoichiometry. Since oxides are prone to reduce the oxygen content and to alter the cation ratio under such growth conditions, it suggests that the cation and oxygen stoichiometries in complex oxide thin films can be improved by properly optimizing the growth parameters.     

The effect of oxygen pressure on the microstructures of Co-doped rutile TiO2 thin films grown by pulsed laser deposition

Comprehensive microstructures of 7% cobalt-doped rutile TiO₂ thin films grown on c-plane sapphire by pulsed laser deposition were characterized using transmission electron microscopy (TEM). The effects of oxygen pressure during growth on the Co distribution inside the films were investigated, and the detailed growth mechanism of both TiO₂ and TiO₂+Co was discussed. The similar oxygen sublattices and low mismatch between (1 0 0) rutile and c-plane sapphire favors the rutile phase. However, the three-fold symmetry of the substrate surface resulted in three rutile domain orientation variants, and they grow adjacent to each other. Cobalt was found to precipitate out as nanocrystals inside the TiO₂ matrix as the growth pressure of oxygen was decreased. At 0.05 mTorr oxygen pressure, almost all of the Co segregates into crystallographically aligned nanocrystals with a particle size of 4.4±0.15 nm. All the samples have magnetic coercivity at room temperature. The magnetic moment per Co atom increased with decreased oxygen pressure, suggesting that the Co that replaced the Ti²⁺ in the TiO₂ lattice does not have a large magnetic moment.     

Synchrotron X-ray diffraction studies of heteroepitaxial ZnO films grown by pulsed laser deposition

Heteroepitaxial ZnO films were grown by pulsed laser deposition on various substrates such as GaN-buffered C-Al₂O₃, C-Al₂O₃, A-Al₂O₃, and R-Al₂O₃. The epitaxy nature of the films was investigated mainly by synchrotron X-ray diffraction. The results showed that the GaN interlayer plays a positive role in growing an unstrained, well-aligned epitaxial ZnO film on the basal plane of Al₂O₃. Importantly, the ZnO film grown on R-Al₂O₃ has two differently aligned domains. The dominant (1 1 0) oriented domain has much better alignment in the in-plane direction than the minor portion of (0 0 1) oriented domain, while in the out-of-plane direction the two domains have almost the same mosaic distribution.     

Heteroepitaxial growth of Cu2O thin film on ZnO by metal organic chemical vapor deposition

Cuprous oxide (Cu₂O) thin films were grown epitaxially on c-axis-oriented polycrystalline zinc oxide (ZnO) thin films by low-pressure metal organic chemical vapor deposition (MOCVD) from Copper(II) hexafluoroacetylacetonate [Cu(C₅HF₆O₂)₂] at various substrate temperatures, between 250 and 400 °C, and pressures, between 0.6 and 2.1 Torr. Polycrystalline thin films of Cu₂O grow as single phase with [1 1 0] axis aligned perpendicular to the ZnO surface and with in-plane rotational alignment due to (2 2 0)_Cu2O(0 0 0 2)_ZnO; [0 0 1]_Cu2O[1 2¯ 1 0]_ZnO epitaxy. The resulting interface is rectifying and may be suitable for oxide-based p–n junction solar cells or diodes.     

Growth and optical absorption spectra of ZnO films grown by pulsed laser deposition

ZnO films on Al₂O₃ substrate were grown by using a pulsed laser deposition method. Through photoluminescence (PL) and X-ray diffraction (XRD) measurements, the optimum growth conditions for the ZnO growth were calculated. The results of the XRD measurement indicate that ZnO film was strongly oriented to the c-axis of hexagonal structure and epitaxially crystallized under constraints created by the substrate. The full-width half-maximum for a theta curve of the (0 0 0 2) peak was 0.201°. Also, from the PL measurement, the grown ZnO film was observed to be a free exciton, which indicates a high quality of epilayer. The Hall mobility and carrier density of the ZnO film at 293 K were estimated to be 299 cm²/V sec and , respectively. The absorption spectra revealed that the temperature dependence of the optical band gap on the ZnO films was − .     

Electron microscopy studies of epitaxial MgB2 superconducting thin films grown by in situ reactive evaporation

The morphology and chemistry of epitaxial MgB₂ thin films grown using reactive Mg evaporation on different substrates have been characterized by transmission electron microscopy methods. For polycrystalline alumina and sapphire substrates with different surface planes, an MgO transition layer was found at the interface region. No such layer was present for films grown on MgO and 4-H SiC substrates, and none of the MgB₂ films had any detectable oxygen incorporation nor MgO inclusions. High-resolution electron microscopy revealed that the growth orientation of the MgB₂ thin films was closely related to the substrate orientation and the nature of the intermediary layer. Electrical measurements showed that very low resistivities (several μΩ cm at 300 K) and high superconducting transition temperatures (38 to 40 K) could be achieved. The correlation of electrical properties with film microstructure is briefly discussed.     

Enhancement of near-band edge photoluminescence of ZnO thin films by employing MgF2 buffer layer

ZnO/MgF₂/ZnO sandwich structure films were fabricated. The effects of a buffer layer on structure and optical properties of ZnO films were investigated by X-ray diffraction, photoluminescence, optical transmittance and absorption measurements. Measurement results showed that the buffer layer had the effects of improving the quality of ZnO films and releasing the residual stresses in the films. The near-band edge emissions of ZnO films deposited on the MgF₂ buffer layer were significantly enhanced compared with those deposited on bare substrate due to the smaller lattice mismatch between MgF₂ and ZnO than that between fused silica and ZnO.     

Growth of epitaxial thin films of scandium nitride on 100-oriented silicon

A series of 100-oriented ScN films was grown under N-rich conditions on 100-oriented Si using different Sc fluxes. The ScN films grew in an epitaxial cube-on-cube orientation, with [0 0 1]_ScN//[0 0 1]_Si and [1 0 0]_ScN//[1 0 0]_Si, despite the high (11%) lattice mismatch between ScN and Si. The film grain size increases and the film ω-FWHM decreases with increasing Sc flux, but the film roughness increases. Films grown under similar conditions on 111-oriented Si resulted in mixed 111 and 100 orientations, indicating that the 100 orientation is favoured both due to texture inheritance from the substrate and due to the growth conditions used.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

Epitaxial growth of the CoFe2O4 film on SrTiO3 and its characterization

Cobalt ferrite (CoFe₂O₄) thin film is epitaxially grown on (0 0 1) SrTiO₃ (STO) by laser molecular beam epitaxy (LMBE). The growth modes of CoFe₂O₄ (CFO) film are found to be sensitive to laser repetition, the transitions from layer-by-layer mode to Stranski–Krastanov (SK) mode and then to island mode occur at the laser repetition of 3 and 5 Hz at 700 °C, respectively. The X-ray diffraction (XRD) results show that the CFO film on (0 0 1) SrTiO₃ is compressively strained by the underlying substrate and exhibits high crystallinity with a full-width at half-maximum of 0.86°. Microstructural studies indicate that the as-deposited CFO film is c-oriented island structure with rough surface morphology and the magnetic measurements reveal that the compressive strained CoFe₂O₄ film exhibits an enhanced out-of-plane magnetization (190 emu/cm³) with a large coercivity (3.8 kOe).     

Synthesis and characteristics of Na-doped Bi4Ti3O12 thin films on Si substrate

Bi_3.25Na_2.25Ti₃O₁₂ thin films were prepared on p-Si(1 1 1) substrate by a metalorganic solution decomposition (MOSD) method. The structural characteristic and crystallization of the films were examined by X-ray diffraction. The current–voltage characteristic shows ohmic conductivity in the lower voltage range and space-charge-limited conductivity in the higher voltage range. The dielectric constant is 53 at a frequency of 100 kHz at room temperature and the dissipation factor exists at a minimal value of 0.02 at a frequency of 200 kHz. The retention time estimated by measuring capacitance is about 10⁶ s. Nonhysteretic C–V curves at various frequencies were also collected.     

Influence of cooling rate on the liquid-phase epitaxial growth of Zn3P2

We report the liquid-phase epitaxial growth of Zn₃P₂ on InP (1 0 0) substrates by conventional horizontal sliding boat system using 100% In solvent. Different cooling rates of 0.2–1.0 °C/min have been adopted and the influence of supercooling on the properties of the grown epilayers is analyzed. The crystal structure and quality of the grown epilayers have been studied by X-ray diffraction and high-resolution X-ray rocking measurements, which revealed a good lattice matching between the epilayers and the substrate. The supercooling-induced morphologies and composition of the epilayers were studied by scanning electron microscopy and energy dispersive X-ray analysis. The growth rate has been calculated and found that there exists a linear dependence between the growth rate and the cooling rate. Hall measurements showed that the grown layers are unintentionally doped p-type with a carrier mobility as high as 450 cm²/V s and a carrier concentration of 2.81×10¹⁸ cm⁻³ for the layers grown from 6 °C supercooled melt from the cooling rate of 0.4 °C/min.     

Growth and characterization of nanostructured Al2O3/YAG/ZrO2 hypereutectics with large surfaces under laser rapid solidification

The preparation of large bulk oxide eutectics with homogeneous and dense structure in nano-scale by melt growth method is a difficult challenge. Fully dense, homogeneous and crack-free ternary nanostructured Al₂O₃/YAG/ZrO₂ hypereutectic plate with large surface is successfully obtained by laser remelting. The hypereutectic in selected composition presents an ultra-fine eutectic-like microstructure consisting of alternating interpenetrating Al₂O₃, YAG and ZrO₂ lamellae with mean interphase spacing of about 150 nm, which is much smaller than the ternary eutectic composition grown at the same growth conditions. With the increase of laser scanning rate, the lamellar spacing is rapidly decreased. The minimum value obtained is 50 nm. The analysis indicates that the strong faceted growth behavior and cooperative branching of the component phases related with high entropies of fusion and large kinetic undercooling during laser rapid solidification are the primary formation reasons for the irregular eutectic growth morphology. Furthermore, the unique cellular microstructure with complex structure is also observed at high growth rate, and their formation mechanism and effect of the composition on the microstructure are discussed.     

High-resolution electron microscopy of microstructure of SrTiO3/BaZrO3 bilayer thin films on MgO substrates

SrTiO₃/BaZrO₃ heterofilms as buffer layers are deposited on (0 0 1) MgO substrates by an RF-sputtering technique. The atomic structure and the defect configuration at the interfaces are investigated by means of aberration-corrected high-resolution transmission electron microscopy. At the BaZrO₃/MgO interface, two types of interfacial structures, MgO/ZrO₂-type and MgO/BaO-type, are observed. Antiphase boundaries and dislocations are found at the BaZrO₃/MgO interface. The formation of these lattice defects is discussed in terms of film growth and structural imperfections of the substrate surface. At the SrTiO₃/BaZrO₃ interface, a high density of misfit dislocations is observed with different configurations. The formation of these dislocations contributes both to the relaxation of the large misfit strain and to stopping of the further propagation of lattice defects which are formed in the BaZrO₃ layer into the SrTiO₃ layer.     

Sn3O4 single crystal nanobelts grown by carbothermal reduction process

This article reports on the growth of single crystal Sn₃O₄ nanobelts and SnO by a carbothermal reduction process in two different regions of a furnace tube. Even though intermediate tin oxide compounds (Sn₃O₄) have been observed experimentally, the study of structures based on them is a challenging task. Characterization data allowed us to propose that Sn₃O₄ nanobelts grew by vapor–solid mechanism while SnO grew by self-catalyst vapor–liquid–solid mechanism. Electrical measurements of a single Sn₃O₄ nanobelt were performed at different temperatures, revealing undoped semiconductor characteristics.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

High-temperature conductivity in chemical bath deposited copper selenide thin films

This paper reports high-temperature (305–523 K) electrical studies of chemical bath deposited copper (I) selenide (Cu_2−xSe) and copper (II) selenide (Cu₃Se₂) thin films. Cu_2−xSe and Cu₃Se₂ have been prepared on glass substrates from the same chemical bath at room temperature by controlling the pH. From X-ray diffraction (XRD) profiles, it has been found that Cu_2−xSe and Cu₃Se₂ have cubic and tetragonal structures, respectively. The composition of the chemical constituent in the films has been confirmed from XRD data and energy-dispersive X-ray analysis (EDAX). It has been found that both phases of copper selenide thin films have thermally activated conduction in the high-temperature range. In this paper we also report the variation of electrical parameters with film thickness and the applied voltage.