Growth and structural properties of crystalline LaAlO3 on Si (0 0 1)

Crystalline LaAlO₃ was grown by oxide molecular beam epitaxy (MBE) on Si (0 0 1) surfaces utilizing a 2 ML SrTiO₃ buffer layer. This SrTiO₃ buffer layer, also grown by oxide MBE, formed an abrupt interface with the silicon. No SiO₂ layer was detectable at the oxide-silicon interface when studied by cross-sectional transmission electron microscopy. The crystalline quality of the LaAlO₃ was assessed during and after growth by reflection high energy electron diffraction, indicating epitaxial growth with the LaAlO₃ unit cell rotated 45° relative to the silicon unit cell. X-ray diffraction indicates a (0 0 1) oriented single-crystalline LaAlO₃ film with a rocking curve of 0.15° and no secondary phases. The use of SrTiO₃ buffer layers on silicon allows perovskite oxides which otherwise would be incompatible with silicon to be integrated onto a silicon platform.     

Effective formation of interface controlled Y2O3 thin film on Si(1 0 0) in a metal-(ferroelectric)-insulator-semiconductor structure

Yttrium was deposited on the chemical oxide of Si and annealed under vacuum to control the interface for the formation of Y₂O₃ as an insulating barrier to construct a metal-ferroelectric-insulator-semiconductor structure. Two different pre-annealing temperatures of 600 and 700 °C were chosen to investigate the effect of the interface state formed after the pre-annealing step on the successive formation of Y₂O₃ insulator and Nd₂Ti₂O₇ (NTO) ferroelectric layer through annealing under an oxygen atmosphere at 800 °C. Pre-anneal treatments of Y-metal/chemical-SiO₂/Si at 600 and 700 °C induced a formation of Y₂O₃ and Y-silicate, respectively. The difference in the pre-anneal temperature induced almost no change in the electrical properties of the Y₂O₃/interface/Si system, but degraded properties were observed in the NTO/Y₂O₃/interface/Si system pre-annealed at 600 °C when compared with the sample pre-annealed at 700 °C. C-V characteristics of the NTO/Y₂O₃/Si structured system showed a clockwise direction of hysteresis, and this gap could be used as a memory window for a ferroelectric-gate. A smaller hysteric gap and electrical breakdown values were observed in the NTO/Y₂O₃/Si system pre-annealed at 600 °C, and this was due to an unintentional distribution of the applied field from the presence of an interfacial layer containing Y-silicate and SiO₂ phases.     

Epitaxial growth of Dy2O3 thin films on epitaxial Dy-germanide films on Ge(0 0 1) substrates

Ultra-thin films of Dy are grown on Ge(0 0 1) substrates by molecular beam deposition near room temperature and immediately annealed for solid phase epitaxy at higher temperatures, leading to the formation of DyGe_x films. Thin films of Dy₂O₃ are grown on the DyGe_x film on Ge(0 0 1) substrates by molecular beam epitaxy. Streaky reflection high energy electron diffraction (RHEED) patterns reveal that epitaxial DyGe_x films grow on Ge(0 0 1) substrates with flat surfaces. X-ray diffraction (XRD) spectrum suggests the growth of an orthorhombic phase of DyGe_x films with (0 0 1) orientations. After the growth of Dy₂O₃ films, there is a change in RHEED patterns to spotty features, revealing the growth of 3D crystalline islands. XRD spectrum shows the presence of a cubic phase with (1 0 0) and (1 1 1) orientations. Atomic force microscopy image shows that the surface morphology of Dy₂O₃ films is smooth with a root mean square roughness of 10 Å.     

Highly (1 0 0)-oriented Pb(Zr0.20Ti0.80)O3/(Pb1−xLax)Ti1−x/4O3 multilayered thin films prepared by RF magnetron sputtering

The Pb(Zr_0.20Ti_0.80)O₃/(Pb_1−xLa_x)Ti_1−x/4O₃ (x = 0, 0.10, 0.15, 0.20) (PZT/PLT_x) multilayered thin films were in situ deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering technique with a PbO_x buffer layer. With this method, all PZT/PLT_x multilayered thin films possess highly (1 0 0) orientation. The PbO_x buffer layer leads to the (1 0 0) orientation of the multilayered thin films. The effect of the La content in PLT_x layers on the dielectric and ferroelectric properties of the PZT multilayered thin films was systematically investigated. The enhanced dielectric and ferroelectric properties are observed in the PZT/PLT_x (x = 0.15) multilayered thin films. The dielectric constant reaches maximum value of 365 at 1 KHz for x = 0.15 with a low loss tangent of 0.0301. Along with enhanced dielectric properties, the multilayered thin films also exhibit large remnant polarization value of 2P_r = 76.5 μC/cm², and low coercive field of 2E_c = 238 KV/cm.     

Dielectric enhancement in interface-modified BaTiO3/SrTiO3 multilayered films prepared by pulsed laser deposition

Pulsed-laser-deposited polycrystalline BaTiO₃/SrTiO₃ multilayered films on Pt/Ti/SiO₂/Si substrates have been fabricated with interfacial modification through lowering the oxygen pressure during the time interval in between two adjacent depositions. It is found that the formation of the heterolayered structure is essential to get the dielectric enhancement. Such heterolayered films have large dielectric constant of 1201 with a loss tangent below 0.1 at 10 KHz. This is about two times that of the identically prepared Ba_0.5Sr_0.5TiO₃/Ba_0.5Sr_0.5TiO₃ homolayered and uniform Ba_0.5Sr_0.5TiO₃ films. The enhancement of dielectric properties is attributed to the presence of the interfacial regions with controllable space charges due to the formation of oxygen vacancies at lower oxygen pressure.     

The electronic structures and optical properties of BaTiO3 and SrTiO3 using first-principles calculations

The electronic-energy band structures and total density of states (TDOS) for bulk BaTiO₃ and SrTiO₃ were calculated by the first-principles calculations using density-functional theory and local-density approximation. The calculated band structure of BaTiO₃ and SrTiO₃ show the energy band gaps of 1.81 and 1.92 eV at the Γ point in the Brillouin zone, respectively. The optical properties of the both perovskites in the core-level spectra are investigated by the first principles under scissor approximation. The optical constants like refractive index and extinction coefficient of both BaTiO₃ and SrTiO₃ were derived from the calculated real and imaginary parts of the dielectric function. The calculated spectra were compared with the experimental results for BaTiO₃, SrTiO₃ in good agreement.     

Photoemission (XPS and XPD) study of epitaxial LaAlO3 film grown on SrTiO3(0 0 1)

This study investigates the tensile-strained growth of LaAlO₃ on SrTiO₃(0 0 1) substrate by molecular beam epitaxy (MBE). Growth was controlled in situ by reflection high energy electron diffraction (RHEED). The characterization was carried out ex situ by photoemission and atomic force microscopy (AFM). Photoelectron spectroscopy (XPS) reveals the development of a TiO_x-rich interface. Photoelectron diffraction (XPD) confirms that a 1.2-nm-thick pseudomorphic LaAlO₃ film has been grown on SrTiO₃(0 0 1) substrate with a perpendicular lattice parameter of 0.372±0.02 nm.     

Direct epitaxial growth of InP based heterostructures on SrTiO3/Si(0 0 1) crystalline templates

A study of the structural and optical properties of an InAsP/InP quantum well heterostructure grown on a crystalline SrTiO₃ (STO)/Si(0 0 1) template is presented. The mismatch between InP and STO is fully accommodated by an array of geometric dislocations confined at the heterointerface. As a consequence, InP takes its bulk lattice parameter as soon as growth begins, and does not contain threading dislocations related to plastic relaxation. It contains twins related to the initially three-dimensional growth. Despite these twins, photoluminescence from the quantum well is detected at room temperature, showing that STO/Si(0 0 1) templates have an interesting potential for the monolithic integration of III-V semiconductors on silicon.     

In situ atomic layer deposition and synchrotron-radiation photoemission study of Al2O3 on pristine n-GaAs(0 0 1)-4 × 6 surface

This work presents the in situ reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM) and synchrotron-radiation photoemission studies for the morphological and interfacial chemical characterization of in situ atomic layer deposited (ALD) Al₂O₃ on pristine molecular beam epitaxy (MBE) grown Ga-rich n-GaAs (1 0 0)-4 × 6 surface. Both the RHEED pattern and STM image demonstrated that the first cycle of ALD-Al₂O₃ process reacted immediately with the GaAs surface. As revealed by in situ synchrotron-radiation photoemission studies, two types of surface As atoms that have excess in charge in the clean surface served as reaction sites with TMA. Two oxidized states were then induced in the As 3d core-level spectra with chemical shifts of +660 meV and +1.03 eV, respectively.     

Epitaxial growth of LaAlO3 on Si(0 0 1) using interface engineering

In this work, the potentiality of molecular beam epitaxy techniques to prepare epitaxial lanthanum aluminate (LaAlO₃) films on Si(0 0 1) is explored. We first demonstrate that the direct growth of LaAlO₃ on Si(0 0 1) is impossible : amorphous layers are obtained at temperatures below 600 °C whereas crystalline layers can be grown at higher temperatures but interfacial reactions leading to silicate formation occur. An interface engineering strategy is then developed to avoid these reactions. SrO and SrTiO₃ have been studied as buffer for the subsequent growth of LaAlO₃. Only partial LaAlO₃ epitaxy is obtained on SrO whereas high quality layers are achieved on SrTiO₃. However both SrO and SrTiO₃ appear to be unstable with respect of Si at the growth temperature of LaAlO₃ (700 °C). This leads to the formation of relatively thick amorphous interfacial layers. Despite their instability at high temperature, these processes could be used for the fabrication of twins-free LaAlO₃ templates on Si, and for the fabrication of complex oxide/Si heterostructures for various applications.     

Direct measurement of interfacial structure in epitaxial Gd2O3 on GaAs (0 0 1) using scanning tunneling microscopy

The epitaxial growth of Gd₂O₃ on GaAs (0 0 1) has given a low interfacial density of states, resulting in the demonstration of the first inversion-channel GaAs metal-oxide-semiconductor field-effect transistor. Motivated by the significance of this discovery, in this work, cross-sectional scanning tunneling microscopy is employed herein to obtain precise structural and electronic information on these epitaxial films and interfaces. At the interface, the interfacial stacking of Gd₂O₃ films is directly correlated with the stacking sequence of the substrate GaAs. Additionally, from the local electronic states across the gate oxides, the spatial extent of the GaAs wavefunctions into the oxide dielectric may suggest a minimum Gd₂O₃ thickness to be of bulk properties.     

Influence of La substitution on the electrical properties of metal-ferroelectric (BiFeO3)-insulator (CeO2)-semiconductor nonvolatile memory structures

Metal-multiferroic (La-substituted BiFeO₃)-insulator (CeO₂)-semiconductor (MFIS) capacitors has been fabricated. The crystalline phase and amount of La³⁺ substitution at Bi-site were investigated by XRD and XPS in the postannealing temperature range from 500 to 700 °C, respectively. The microstructure and interfacial layer between CeO₂ and Si substrate were characterized by HRTEM. The memory windows as functions of insulator film thickness and DC power for La were measured. The maximum memory window is about 1.9 V under ±6 V applied voltage. The ferroelectric polarization increases with increasing substitution amount. The morphologies of La-substituted BiFeO₃ films were also studied by AFM.     

Fabrication and electrical characteristics of ultrathin (HfO2)x(SiO2)1−x films by surface sol-gel method and reaction-anneal treatment

Hafnium oxide (HfO₂) films were deposited on Si substrates with a pre-grown oxide layer using hafnium chloride (HfCl₄) source by surface sol-gel process, then ultrathin (HfO₂)_x(SiO₂)_1−x films were fabricated due to the reaction of SiO₂ layer with HfO₂ under the appropriate reaction-anneal treatment. The observation of high-resolution transmission electron microscopy indicates that the ultrathin films show amorphous nature. X-ray photoelectron spectroscopy analyses reveal that surface sol-gel derived ultrathin films are Hf-Si-O alloy instead of HfO₂ and pre-grown SiO₂ layer, and the composition was Hf_0.52Si_0.48O₂ under 500 °C reaction-anneal. The lowest equivalent oxide thickness (EOT) value of 0.9 nm of film annealed at 500 °C has been obtained with small flatband voltage of −0.31 V. The experimental results indicate that a simple and feasible solution route to fabricate (HfO₂)_x(SiO₂)_1−x composite films has been developed by means of combination of surface sol-gel and reaction-anneal treatment.     

Microstructure and dielectric response of SrTiO3/NdGaO3 interdigitated capacitors

Epitaxial strontium titanate (SrTiO₃ or STO) thin films were prepared by an off-axis pulsed laser deposition technique on neodymium gallate (NdGaO₃ or NGO) substrates held at temperature of 820 °C. This technique allows different film growth rates in a deposition. Coplanar capacitors were fabricated and dielectric responses were measured at 1 MHz and at 2 GHz, and from 300 K to 4 K. The electric field tunability of the dielectric constant and loss tangent were taken with a range of electric field. The structure and morphology of the films were analyzed using high-resolution X-ray diffractometry and atomic force microscopy, respectively. The results showed that the films are crystalline with (1 0 0) orientation and the grains are columnar. Increased in-plane grain size and reduced surface to volume ratio were found to play a major role in improved performance of the film coplanar capacitors. The film with the growth rate of approximate 40 Å/min showed the highest change in the dielectric constant with an electric field of 4 V/μm. The film also showed the largest in-plane grain size of about 3000 Å.     

Occurrence of ferroelectricity in epitaxial BiMnO3 thin films

In this paper, we report evidence of ferroelectricity in perovskite manganite (BiMnO₃) thin films synthesized via r.f. magnetron sputtering method on a single-crystal (1 0 0)-oriented SrTiO₃:Nb 0.1% and Pt/TiO₂/SiO₂/Si substrates. X-ray diffraction measurements were used to analyse the crystal structure of the thin films, revealing epitaxial growth for BiMnO₃ films with their (1 1 1) and (2 2 2) planes parallel to the (0 0 1) and (0 0 2) planes of the SrTiO₃ substrate. AFM measurements were performed to investigate surface morphology; quantitative values of roughness and grain size are in the range between 300 and 500 nm. Ferroelectric characterization was conducted at low temperatures and at 300 K. Hysteresis loops (polarization vs. voltage) were obtained, showing saturation polarizations of , and at 105, 122, and 300 K. Resistance vs. temperature measurements were performed, which indicated this to be very robust insulating material.     

A novel thermally-stable zirconium amidinate ALD precursor for ZrO2 thin films

ZrO₂ thin films were deposited by the atomic layer deposition process on Si substrates using tetrakis(N,N′-dimethylacetamidinate) zirconium (Zr-AMD) as a Zr precursor and H₂O as an oxidizing agent. Tetrakis (ethylmethylamino) zirconium (TEMA-Zr) was also evaluated for a comparative study. Physical properties of ALD-derived ZrO₂ thin films were studied using ellipsometry, grazing incidence XRD (GI-XRD), high resolution TEM (HRTEM), and atomic force microscopy (AFM). The ZrO₂ deposited using Zr-AMD showed a better thermal stability at high substrate temperature (>300 °C) compared to that using TEMA-Zr. GI-XRD analysis reveals that after 700 °C anneal both ZrO₂ films enter tetragonal phase. The electrical properties of N₂-annealed ZrO₂ film using Zr-AMD exhibit an EOT of 1.2 nm with leakage current density as low as 2 × 10⁻³ A/cm² (@V_fb−1 V). The new Zr amidinate is a promising ALD precursor for high-k dielectric applications.     

Effects of annealing schedule on orientations of Bi3.2Nd0.8Ti3O12 ferroelectric films prepared by metalorganic solution deposition

Fatigue-free Bi_3.2Nd_0.8Ti₃O₁₂ ferroelectric thin films were successfully prepared on p-Si(1 1 1) substrate using metalorganic solution deposition process. The orientation and formation of thin film under different annealing schedules were studied using XRD and AFM. XRD analysis indicated that (2 0 0)-oriented films with degree of orientation of I₍₂₀₀₎/I₍₁₁₇₎ = 2.097 and 0.466 were obtained by preannealing the film at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min, 10 min and 20 min, respectively, (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 1.706 were obtained by rapid thermal annealing the film at 700 °C for 3 min without preannealing, and (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 0.719 were obtained by preheating the film from room temperature to 700 °C at 20 °C/min followed by annealing for 10 min. The a-axis and c-axis orientation decreased as increase in annealing time due to effects of (1 1 1)-oriented substrate. AFM analysis further indicated that preannealing at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min resulted in formation of platelike crystallite parallel to substrate surface, however rapid thermal annealing at 700 °C for 3 min without preannealing resulted in columnar crystallite perpendicular to substrate surface.     

Band offsets at the (1 0 0)GaSb/Al2O3 interface from internal electron photoemission study

From electron internal photoemission and photoconductivity measurements at the (1 0 0)GaSb/Al₂O₃ interface, the top of the GaSb valence band is found to be 3.05 ± 0.10 eV below the bottom of the Al₂O₃ conduction band. This interface band alignment corresponds to conduction and valence band offsets of 2.3 ± 0.10 eV and 3.05 ± 0.15 eV, respectively, indicating that the valence band in GaSb lies energetically well above the valence band of In_xGa_1−xAs (0 ? x ? 0.53) or InP.     

Low temperature sintering properties of Y-doped BaTiO3 ceramics by BaB2O4 sintering aid

The sintering process of semiconducting Y-doped BaTiO₃ ceramics added with BaB₂O₄ as low temperature sintering aid were investigated. When the low temperature sintering aid BaB₂O₄ added Y-doped BaTiO₃ ceramics prepared by Sol-Gel method, the sintering temperature of BaTiO₃-based ceramics would be greatly decreased, and also widen sintering range. Y-doped BaTiO₃ ceramics with BaB₂O₄ addition can be obtained at 1050 °C. Ceramics samples with room temperature resistivity 60-80 Ω cm, ratio of the maximum resistivity to minimum resistance (Rmax/Rmin) 10⁴ and temperature coefficient of resistivity (α) 10%/°C were obtained.     

Characterization of crystalline MOCVD SrTiO3 films on SiO2/Si(100)

SrTiO₃ thin films (STO), were deposited on Si(100) covered by 2 nm of SiO₂, at different temperatures from 450 °C to 850 °C using liquid injection MOCVD, the bimetallic precursor being Sr₂Ti₂(OiPr)₈(tmhd)₄. The STO films were analysed by XRD, FTIR, SIMS and TEM. An amorphous layer was observed between STO and SiO₂/Si. The nature and thickness of the interlayer were determined, as well as the most favourable conditions for a good quality crystalline STO film, and a reduced interlayer.