Properties of LiNbO3 based heterostructures grown by pulsed-laser deposition for optical waveguiding application

Epitaxial LiNbO₃ (LN) thin films have been grown onto (00.1) Al₂O₃ substrates and onto sapphire covered with a conductive ZnO buffer layer. For the two systems, the LN thin films are well crystallised and highly (00.1) oriented. Epitaxial relationships between the different layers are evidenced both on the LN/sapphire film and the LN/ZnO/sapphire heterostructure. The optical waveguiding propagation losses of the LN/sapphire films are very low (1 ± 0.5 dB/cm) while the LN/ZnO/sapphire heterostructure does not exhibit satisfying waveguiding properties mainly due to the high conductivity (600 S m^− 1) of the ZnO buffer layer.     

The preparation of Zn-ferrite epitaxial thin film from epitaxial Fe3O4:ZnO multilayers by ion beam sputtering deposition

A new method to grow a well-ordered epitaxial ZnFe₂O₄ thin film on Al₂O₃(0001) substrate is described in this work. The samples were made by annealing the ZnO/Fe₃O₄ multilayer which was grown with low energy ion beam sputtering deposition. Both the Fe₃O₄ and ZnO layers were found grown epitaxially at low temperature and an epitaxial ZnFe₂O₄ thin film was formed after annealing at 1000 °C. X-ray diffraction shows the ZnFe₂O₄ film is grown with an orientation of ZnFe₂O₄(111)//Al₂O₃(0001) and ZnFe₂O₄(1-10)//Al₂O₃(11-20). X-ray absorption spectroscopy studies show that Zn²⁺ atoms replace the tetrahedral Fe²⁺ atoms in Fe₃O₄ during the annealing. The magnetic properties measured by vibrating sample magnetometer show that the saturation magnetization of ZnFe₂O₄ grown from ZnO/Fe₃O₄ multilayer reaches the bulk value after the annealing process.     

Electron transport in InGaO3(ZnO)m (m=integer) studied using single-crystalline thin films and transparent MISFETs

We have investigated the characteristics of transparent metal-insulator-semiconductor field-effect transistors (MISFETs) fabricated using InGaO₃(ZnO)_m (m=integer) single-crystalline thin films as n-channel layers and amorphous alumina as gate insulator films. The MISFETs exhibit good characteristics such as insensitivity to visible light illumination, off-current as low as ∼1 nA with a positive threshold voltage of ∼3 V and on/off current ratio of 10⁵. The field-effect mobility increased from ∼1 to ∼10 cm² (V s)⁻¹ as the m-value increased. Room temperature Hall mobility also increased. However, unexpectedly these values were lower than the field-effect mobility. It is explained by existence of shallow localized state in the homologous compounds.     

Structural and thermal characterization of La5Ca9Cu24O41 thin films grown by pulsed laser deposition on (1 1 0) SrTiO3 substrates

In the present study stoichiometric, b-axis oriented La₅Ca₉Cu₂₄O₄₁ thin films were grown by pulsed laser deposition on (1 1 0) SrTiO₃ substrates in the temperature range 600-750 °C. High resolution transmission electron microscopy was employed to investigate the growth mechanism and the epitaxial relationship between the SrTiO₃ substrates and the La₅Ca₉Cu₂₄O₄₁ films grown at 700 °C. The 3-ω method was used to measure the cross-plane thermal conductivity of La₅Ca₉Cu₂₄O₄₁ films in the temperature range 50-350 K. The observed glass-like behavior is attributed to atomic-scale defects, grain boundaries and an interfacial layer formed between film and substrate.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

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.     

Atomic layer deposition grown composite dielectric oxides and ZnO for transparent electronic applications

In this paper, we report on transparent transistor obtained using laminar structure of two high-k dielectric oxides (hafnium dioxide, HfO₂ and aluminum oxide, Al₂O₃) and zinc oxide (ZnO) layer grown at low temperature (60 °C-100 °C) using Atomic Layer Deposition (ALD) technology. Our research was focused on the optimization of technological parameters for composite layers Al₂O₃/HfO₂/Al₂O₃ for thin film transistor structures with ZnO as a channel and a gate layer. We elaborate on the ALD growth of these oxides, finding that the 100 nm thick layers of HfO₂ and Al₂O₃ exhibit fine surface flatness and required amorphous microstructure. Growth parameters are optimized for the monolayer growth mode and maximum smoothness required for gating.     

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.     

Fabrication of highly conductive Ta-doped SnO2 polycrystalline films on glass using seed-layer technique by pulse laser deposition

We discuss the fabrication of highly conductive Ta-doped SnO₂ (Sn_1 − xTa_xO₂; TTO) thin films on glass by pulse laser deposition. On the basis of the comparison of X-ray diffraction patterns and resistivity (ρ) values between epitaxial films and polycrystalline films deposited on bare glass, we proposed the use of seed-layers for improving the conductivity of the TTO polycrystalline films. We investigated the use of rutile TiO₂ and NbO₂ as seed-layers; these are isostructural materials of SnO_2, which are expected to promote epitaxial-like growth of the TTO films. The films prepared on the 10-nm-thick seed-layers exhibited preferential growth of the TTO (110) plane. The TTO film with x = 0.05 on rutile TiO₂ exhibited ρ  = 3.5 × 10^− 4 Ω cm, which is similar to those of the epitaxial films grown on Al₂O₃ (0001).     

Deposition, characterization and biological application of epitaxial Li:ZnO/Al:ZnO double-layers

Double-layers of lithium doped ZnO (LZO) and aluminum doped ZnO (AZO) are grown on r-cut sapphire (r-Al₂O₃) crystal substrates by pulsed-laser deposition. The epitaxial double-layers are a-axis lattice oriented to the substrate. The LZO/AZO/r-Al₂O₃ samples have high optical transmission in the visible range and a bandgap energy of E_g = 3.28 eV according to the absorption edge of ZnO. The AZO bottom layers are electrically conductive (resistivity at room temperature ρ ~ 10^− 3 Ω cm) and LZO top layers are highly resistive (ρ ≥ 10⁵ Ω cm). Acoustic shear mode resonances in r-Al₂O₃ are excited by employing electric fields to the piezoelectric LZO layer (frequency interval 1.5-3 GHz). For biological applications, Madin-Darby canine kidney cells are cultivated on Platinum coated LZO/AZO/r-Al₂O₃ samples. Osmotic pressure applied to the cells increases or reduces the cell volume depending on the osmolarity of the medium.     

Fabrication of KTa0.65Nb0.35O3 film by pulsed laser deposition on glass substrate with various buffer layers

KTa_0.65Nb_0.35O₃ (KTN) thin films were deposited on amorphous glass substrates using a range of single buffer layers such as indium tin oxide (ITO), zinc oxide (ZnO), 3 at% Al-doped ZnO (AZO), and 3 at% Ga-doped ZnO (GZO), as well as a variety of multi-buffer layers such as SrTiO₃ (STO)/ITO, STO/ZnO, STO/AZO, and STO/GZO using a pulsed laser deposition system. All films showed a polycrystalline perovskite phase with the exception of all single buffer layers and STO/ITO multi-buffer layers. The STO buffer layer is important for crystallizing KTN films due to the similar lattice constant and same crystal structure. The optical transmittance of all films exhibited a transmittance ?90% in the wavelength range.     

Sputter-epitaxy and electric properties of multiferroic Bim + 1Fem-3Ti3O3m + 3 thin films

Growth conditions suitable for sputter-epitaxy of Bi_m + 1Fe_m-3Ti₃O_3m + 3 (BFTO) thin films with layered structure have been investigated. The amount of oxygen during deposition was found to be specifically essential for obtaining a good-quality thin film of BFTO with a large m. The (001) epitaxial thin films of BFTO with m of nearly 10 which is expected to retain magnetic order up to room temperature have been successfully grown on (001) SrTiO₃ substrates under the determined optimum condition. The film exhibited leakage current as low as order of 10⁻²-10⁻¹ A/m² limited by Schottky emission at the interfaces between the electrodes and the film. In addition, the film showed a ferroelectric polarization curve with Pr = 6 μC/cm² for applied field of 35 MV/m at room temperature though the curve was unsaturated. These indicate that the BFTO (m = 10) thin films are promising as multiferroics at room temperature.     

Structural and optical analysis of nanocrystalline thin films of mixed rare earth oxides (Y1-xErx)2O3

Nanocrystalline thin films of mixed rare earth oxides (Y_1-xEr_x)₂O₃(0.1 ≤ x ≤ 1) were deposited by electron beam evaporation technique on polished fused silica glass at different substrate temperatures (200-500 °C). The effect of the substrate temperature as well as the mixing parameter (x) on the structural and optical properties of these films has been investigated by using X-ray diffraction (XRD), energy dispersive x-ray analysis and optical spectrophotometry. XRD investigation shows that mixed rare earth oxides film (Y_1-xEr_x)₂O₃ grown at lower substrate temperature (T_s ≤ 300 °C) are poorly crystalline, whereas films grown at higher substrate temperatures (T_s ≥ 400 °C) tend to have better crystallinity. Furthermore, the mixing parameter (x) was found to stabilize the cubic phase over the entire of 0.1 ≤ x ≤ 1. The crystallite size of the films was found to vary in the range from 25 to 39 nm. Optical band gap of the films was deterimined by analysis of the absoprtion coeffifcient. For films deposited at different substrate temperatures direct and indirect transitions occur with energies varied from 5.29 to 5.94 eV and from 4.23 to 4.51 eV, respectively. However, films of different composition x, give optical band gap varied from 6.14 to 5.86 eV for direct transition and from 5.23 to 4.22 eV for indirect transitions. Consequently, one may conclude that it is possible to tune the energy band gap by relative fraction of constituent oxides. It was found that optical constants increase with increasing the substrate temperature. Nevertheless, the values of n and k decrease with increasing the mixing parameter, x.     

Effects of low temperature ZnO and MgO buffer thicknesses on properties of ZnO films grown on (0001) Al2O3 substrates by plasma-assisted molecular beam epitaxy

We investigated the structural properties of Zn-polar ZnO films with low temperature (LT) ZnO and MgO buffer layers grown by plasma-assisted molecular beam epitaxy on (0001) c-Al₂O₃ substrates using X-ray diffraction and transmission electron microscopy (TEM). The effects of MgO buffer layer thickness and LT ZnO buffer layer thickness were also examined. The optimum thicknesses for better crystal quality were 8 and 40 nm. One-pair and two-pair LT ZnO/MgO buffer layers were employed, and the changes in the structural properties of the high-temperature (HT) ZnO films using such buffer layers were studied. Contrary to the general tendency of c-ZnO films, the HT ZnO films on the LT ZnO/MgO buffer layers showed higher full width at half maximum (FWHM) values for X-ray rocking curves (XRCs) with (0002) reflection than those with (101?1) reflection. Compared with the one-pair LT ZnO/MgO buffer layers, the FWHM values of (0002) XRCs markedly decreased, whereas those of (101?1) XRCs slightly increased due to the insertion of one more pair of LT ZnO/MgO buffer layers into the previous film with one-pair LT ZnO/MgO buffer layers. The cross-sectional TEM observations with the two-beam condition confirmed that the screw dislocation was the dominant threading dislocation type—a finding that agreed well with the XRC results. On the basis of the plan-view TEM observations, the densities of the total threading dislocations for the HT ZnO films with the one- and two-pair LT ZnO/MgO buffer layers were determined as 2.3 × 10⁹ cm^− 2 and 1.6 × 10⁹ cm^− 2, respectively. The results imply that the crystal quality of Zn-polar ZnO films can be improved by two-pair LT ZnO/MgO buffer layers, and types of threading dislocations can be modified by adjusting the buffer system.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.     

Growth and structural investigations of epitaxial hexagonal YMnO3 thin films deposited on wurtzite GaN(001) substrates

Epitaxial hexagonal YMnO₃ (h-YMnO₃) films having sharp (00l) X-ray diffraction peaks were grown above 700 °C in 5 mTorr O₂ via pulsed laser deposition both on as-received wurtzite GaN/AlN/6H-SiC(001) (w-GaN) substrates as well as on w-GaN surfaces that were etched in 50% HF solution. High-resolution transmission electron microscopy revealed an interfacial layer between film and the unetched substrate; this layer was absent in those samples wherein an etched substrate was used. However, the substrate treatment did not affect the epitaxial arrangement between the h-YMnO₃ film and w-GaN substrate. The epitaxial relationships of the h-YMnO₃ films with the w-GaN(001) substrate was determined via X-ray diffraction to be (001)_YMnO3 ‖ (001)_GaN : [11¯0]_YMnO3 ‖ [110]_GaN; in other words, the basal planes of the film and the substrate are aligned parallel to one another, as are the most densely packed directions in planes of the film and the substrate. Interestingly, this arrangement has a larger lattice mismatch than if the principal axes of the unit cells were aligned.     

Study of CuInS2/buffer/ZnO solar cells, with chemically deposited ZnS-In2S3buffer layers

Thin film solar cells based on CuInS₂/buffer/ZnO have been prepared with different buffer layers of mixed ZnS-In₂S₃ composition. The buffer films are grown by chemical bath deposition (CBD) from acidic solutions of InCl₃, ZnSO₄ and thioacetamide (TA). A kinetics study of the growth of the buffer layers is carried out with the quartz crystal microbalance. The influence of bath conditions (solution, temperature and composition) on the growth rate is studied. Films are obtained with different physical, chemical and morphological properties. The absorption coefficient spectra of the films show a variation depending on the CBD conditions, with absorption edges between 2.6 and 3.35 eV. Surface morphology of the films, observed with scanning electron microscopy, reveals that the presence of Zn produces characteristic structures with microtubular form, compared with pure In₂S₃ buffer films. Solar cell results show a significant increase of Voc and FF upon introducing Zn²⁺ ion in the buffer layer.     

Growth and characterization of (Pb,La)(Zr,Ti)O3 thin film epilayers on SrTiO3-buffered Si(001)

Ferroelectric Pb_0.92La_0.08Zr_0.4Ti_0.6O₃ (PLZT) thin films were deposited on SrTiO₃-buffered Si(001) substrate by on-axis radio frequency magnetron sputtering. X-ray diffraction analysis revealed epitaxial growth of monocrystalline PLZT films, with an (001) rocking curve full width at half maximum of ∼ 0.3°. φ-scans showed 45° in-plane orientation of the perovskite unit cell relative to that of silicon. The elemental composition of the thin film heterostructure was examined by Auger sputter depth profiling measurements. The recorded profiles suggest that the SrTiO₃ buffer layer serves not only as a template for epitaxial growth, but also as a barrier suppressing Pb-Si interdiffusion between the PLZT layer and the Si substrate. The surface roughness of the PLZT layer was measured at ∼ 4 nm for films with ∼ 500 nm thickness. Wavelength dispersions for the refractive index (n) and the extinction coefficient (k) were obtained from spectroscopic ellipsometry measurements, with n ∼ 2.48 at the main communication wavelength λ = 1550 nm and k < 0.001 for λ > 650 nm. Recorded polarization vs. electric field loops for the PLZT epilayer, with a SrRuO₃ electrode layer interposed between PLZT and SrTiO₃, showed a remnant polarization P_r ≈ 40 µC/cm² and coercive field E_c ≈ 100 kV/cm. These findings suggest that the sputter-deposited PLZT thin films retain the functional properties critical to ferroelectric and electro-optic device applications, also when integrated on a semiconductor substrate.     

Epitaxial growth of NiTiO3 with a distorted ilmenite structure

MTiO₃ (M = Fe, Mn, Ni) compounds have received recent attention as possible candidates for multiferroic materials capable of magnetization switching by application of an electric field. In an attempt to stabilize NiTiO₃ in the rhombohedral R3 structure, epitaxial Ni_1 − xTi_1 − yO₃ films of different thickness and composition were deposited on Al₂O₃(0001) by pulsed laser deposition, and characterized using several techniques. Structural parameters for ilmenite-type NiTiO₃ and the metastable LiNbO₃-type NiTiO₃ structure with the space group R3c were predicted using density functional theory calculations, and compared with the experimental results. Our structural data from X-ray diffraction and X-ray absorption spectroscopy indicate that epitaxial ilmenite-type NiTiO₃ films were grown. Furthermore, lattice strain exerted by the sapphire substrate results in a distorted ilmenite structure similar to the LiNbO₃-type one. While R3c NiTiO₃, the desired structure based on recent theory, cannot be claimed at this point, our results demonstrate the potential of oxide heteroepitaxy to stabilize metastable multiferroic phases that may be difficult to prepare or are inaccessible in the bulk.