Surface termination of the NdGaO3(1 1 0)

Auger electron spectroscopy using excitation via grazing impact of protons was applied to determine the elemental composition of the topmost and near-surface layers of a NdGaO₃(1 1 0) substrate. The preparation conditions of vicinal NdGaO₃ substrates were optimized by varying the annealing temperature, time, and gas atmosphere. Well prepared surfaces show regularly arranged, atomically smooth terraces with single-atomic steps. The surfaces were always NdO terminated with a small amount of Ga (2-4%) atoms on the surface. A Ga and O depletion layer with a thickness of about 4 nm has been detected at optimized preparation conditions.     

Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Evidence of the primary-color photoluminescence in ion (H,H,C) irradiated and thermal annealed SrTiO3

We have measured photoluminescence (PL) spectrum of (1) thermal-annealed SrTiO₃/Si thin film and undoped SrTiO₃ single crystal; (2) SrTiO₃ single crystal irradiated by high energy (3 MeV) proton, deuterium, and He ion beams and (3) SrTiO₃ single crystal irradiated by low energy (60 keV) H⁺ and C⁻ ions. Two PL emissions are induced in (1) and (2) at visible frequencies 3 and 2.45 eV, while another PL peak is induced at 2 eV in (3). When compared with our previous PL experiments on high-temperature annealed SrTiO₃/SiO₂/Si thin film and 3 MeV proton (H⁺) irradiated STO single crystal, these results confirm that the three PL emissions with blue (3 eV), green (2.45 eV), and red-orange (2 eV) frequencies originate indeed from SrTiO₃. These primary-color PL effect induced at room-temperature makes STO a strong candidate material for future oxide-based optoelectronic application.     

SrTiO3(0 0 1) reconstructions: the (2 × 2) to c(4 × 4) transition

Scanning tunneling microscopy (STM) is used to investigate the (0 0 1) surface structure of Nb doped SrTiO₃ single crystals annealed in ultra high vacuum (UHV). Atomically resolved images of the (2 × 2) reconstructed surface are obtained after annealing a chemically etched sample. With further annealing dotted row domains appear, which coexist with the (2 × 2) reconstruction. The expansion of these domains with further annealing gives rise to the formation of a TiO₂ enriched c(4 × 4) reconstruction.     

Origin of ohmic behavior in Ni, Ni2Si and Pd contacts on n-type SiC

Ni, Ni₂Si and Pd contacts were prepared on n-type 4H-SiC and annealed in the temperature range of 750-1150 °C. The annealed contacts were analyzed before and after acid etching, and different features were found in unetched and etched contacts. Carbon left on the SiC surface after the acid etching of Ni₂Si contacts annealed at 960 °C was highly graphitized. In nickel contacts, the graphitization of interface carbon began at 960 °C and increased after annealing at higher temperatures. In palladium contacts, the onset of the interface carbon graphitization was observed after annealing at 1150 °C. For all three types of metallization, the minimal values of contact resistivity were achieved only when the sharp first-order peak at 1585 cm⁻¹ and distinct second-order peak at ∼2700 cm⁻¹ related to the presence of graphitized carbon were detected by Raman spectroscopy after the acid etching of contacts. The properties of unannealed secondary contacts deposited onto etched primary contacts were similar to the properties of the primary contacts unless carbon was selectively etched. The results show that ohmic behavior of Ni-based and Pd contacts on n-type SiC originates from the formation of graphitic carbon at the interface with SiC.     

Growth and structure of MBE grown TiO2 anatase films with rutile nano-crystallites

We have explored the systematics of TiO₂ polymorph nucleation during film growth by molecular beam epitaxy on perovskite substrates. The accidental lattice match between anatase (0 0 1) and LaAlO₃(0 0 1) or SrTiO₃(0 0 1) typically results in anatase nucleation at the interface. However, the growth conditions dictate whether or not rutile also nucleates, and the associated morphological and structural properties of the composite film. Four symmetry equivalent epitaxial orientations of rutile on anatase are observed when rutile nucleates as discrete particles on LaAlO₃(0 0 1). Such films constitute model systems for studying the anatase/rutile interface, which is of considerable current interest in photochemistry.     

Ferroelectric domain structure of the BiFeO3 film grown on different substrates

Domain structure of BiFeO₃ (BFO) films grown on different substrates, with a conductive La_0.7Sr_0.3MnO₃ underlayer, has been experimentally studied. Two oppositely orientated polarizations, along the long body diagonal to the perovskite unit cell of BFO, are detected in the BFO films on the (0 0 1)-oriented NdGaO₃. Electric pulses applied in the [0 0 1] direction produce a polarization switching, resulting in the domain structure characterized by the 109° domain walls. Contrary to the BFO films on NdGaO₃, the BFO films on SrTiO₃ (0 0 1) exhibit a much complex domain structure. Both 71° and 109° domain walls are possible with a uniform polarization component pointing to the bottom electrode.     

Pulsed laser deposition and characterization of nitrogen-substituted SrTiO3 thin films

Nitrogen-substituted cubic perovskite-type SrTiO₃ thin films were deposited in a one-step process using pulsed reactive crossed beam laser ablation (PRCLA) and RF-plasma assisted pulsed laser deposition (RF-PLD). Both techniques yield preferentially oriented films on SrTiO₃(0 0 1), LaAlO₃(0 0 1) and MgO(0 0 1) substrates with the unit cell parameters within 0.390(5) < a < 0.394(9) nm. The nitrogen content is higher in films deposited by PRCLA (0.84-2.40 at.%) as compared to films deposited by RF-PLD with nitrogen plasma (0.10-0.66 at.%). PRCLA with an ammonia gas pulse leads to a higher nitrogen content compared to the films grown with a nitrogen gas pulse, while films deposited by RF-PLD with ammonia plasma reveal only minor nitrogen contents (<0.10 at.%). The amount of the incorporated nitrogen can be tuned by adjusting the deposition parameters. Films deposited by PRCLA have a lower roughness of 1-3 nm compared to 12-18 nm for the films grown by RF-PLD. PRCLA yields partially reduced films, which exhibit electronic conductivity, while films deposited by RF-PLD are insulating. There is also a pronounced influence of the substrate material on the resistivity of the films deposited by PRCLA: films grown on SrTiO₃ substrates exhibit a metallic-like behaviour, while the corresponding films grown on MgO and LaAlO₃ substrates reveal a metal-to-semiconductor/insulator transition. Nitrogen incorporation into the SrTiO₃ films results in an increased optical absorption at 370-500 nm which is associated with N(2p) localized states with the energy about 0.7 eV higher than the valence band energy in strontium titanate. The optical band gap energies in the studied N-substituted SrTiO₃ films are 3.35-3.40 eV.     

Control of a- and c-plane preferential orientations of ZnO thin films

We report orientation-controllable growth of ZnO thin films and their orientation-dependent electrical characteristics. ZnO thin films were deposited on single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ substrates using pulsed laser deposition (PLD) at different substrate temperatures (400-800 °C). It was found that the orientation of ZnO films could be controlled by using different substrates of single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃. The a-plane () and c-plane (0 0 0 2) oriented ZnO films are formed on LaAlO₃ and SrTiO₃, respectively. In both cases, the degree orientation increased with increasing deposition temperature T_s. Both the surface free energy and the degree of lattice mismatch are ascribed to play an important role for the orientation-controllable growth. Further characterization show that the grain size of the films with both orientations increases for a substrate temperature increase (i.e. from T_s = 400 °C to T_s = 800 °C), whereas the electrical properties of ZnO thin films depend upon their crystalline orientation, showing lower electrical resistivity values for a-plane oriented ZnO films.     

Surface control of optical properties in silicon nanocrystals produced by laser pyrolysis

Macroscopic quantities (g/h) of Si nanoparticles were prepared by laser pyrolysis of silane and showed photoluminescence (PL) emission in the range 700-1050 nm after oxidation in air at a temperature T ≥ 700 °C. Two different strategies were followed to reduce as-produced particle agglomeration which hinders most of the applications, namely etching with either acid or alkaline solutions. Well isolated single particles were detected after acid etching in HF. Disaggregation was also achieved by the combined effect of the high power sonication and alkaline etching by tetra-methyl ammonium hydroxide (TMAH), which leaves OH terminated surfaces. However, in both cases re-aggregation was observed within a few hours after oxide removal. Stable dispersions of Si nanoparticles in different solvents were obtained by treatments of H-terminated surfaces with the surfactant TOPO (C₂₄H₅₁PO, trioctylphospine oxide) and by treatment of OH-terminated surfaces with Na₃PO₄.     

Atomic force microscopy studies of SrTiO<Subscript>3</Subscript> (001) substrates treated by chemical etching and annealing in oxygen

The SrTiO₃ (001) substrates treated by chemical etching in NH₄F-buffered HF solution and annealing in oxygen ambient have been studied by an atomic force microscopy (AFM). The SrTiO₃ substrates with TiO₂-termineted and atomically smooth surfaces and single unit cell steps have been obtained. The surface morphologies of SrTiO₃ substrates strongly depend on the treated conditions and the quality of the substrates.     

Electronic structure and topography of annealed SrTiO3(1 1 1) surfaces studied with MIES and STM

Perovskites of ABO₃ type like strontium titanate (SrTiO₃) are of great practical concern as materials for oxygen sensors operating at high temperatures. It is well known that the surface layer shows different properties compared to the bulk. Numerous studies exist for the SrTiO₃(1 0 0) and (1 1 0) surfaces which have investigated the changes in the electronic structure and topography as a function of the preparation conditions. They have indicated a rather complex behaviour of the surface and the near surface region of SrTiO₃ at elevated temperatures. Up to now, the behaviour of the SrTiO₃(1 1 1) surfaces under thermal treatment is not sufficiently known. This contribution is intended to work out the relation between alteration of the surface topography with respect to the preparation conditions and the simultaneous changes of the electronic structure. We applied scanning tunneling microscopy (STM) to investigate the surface topography and, additionally, metastable impact electron spectroscopy (MIES) to study the surface electronic structure of reconstructed SrTiO₃(1 1 1) surfaces. The crystals were heated up to 1000 °C under reducing and oxidizing conditions. Both preparation conditions cause strong changes of the surface topography and electronic structure. A microfaceting of the topmost layers is found.     

DFT study of Pt adsorption on low index SrTiO3 surfaces: SrTiO3(1 0 0), SrTiO3(1 1 1) and SrTiO3(1 1 0)

Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO₃(1 0 0), SrTiO₃(1 1 1), and SrTiO₃(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO₃(1 1 1) and SrTiO₃(1 1 0), form significantly stronger interfaces than the non-polar SrTiO₃(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface.     

Colossal magnetoresistance effect in epitaxially grown La2/3Ca1/3MnO3 perovskite-like manganite thin films

We report in this work, study on colossal magnetoresistance (CMR) effect in epitaxial La_2/3Ca_1/3 MnO₃ thin films grown on SrTiO₃ (0 0 1) substrates by pulsed laser deposition (PLD) technique. The films were grown on as-received SrTiO₃ substrates and on SrTiO₃ substrates prepared by HF etching (Koster et al., Appl. Phys. Lett. 73 (1998) 2920; V. Leca et al., Wet etching methods for perovskite substrates, University of Twente, MESA+ Research Institute, Low Temperature Division). Two of the samples were annealed in different conditions to investigate the films heat treatment effect on electric and magnetic properties. Electrical resistance was done using the four-probe method at temperatures in the range of 2–375 K without a magnetic field and in an external field of 5 T applied in the film plane. Resistance-magnetic field (R vs. H) at 77 K for the two annealed samples was done in a 5 T sweep magnetic field. The surface morphology and structural information of the films were obtained using atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. Secondary ion mass spectroscopy (SIMS) analysis was performed on the annealed samples to investigate any possible chemical reaction between La_2/3Ca_1/3MnO₃ thin films and SrTiO₃ substrate.     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

Observation of Si(1 0 0) surfaces annealed in hydrogen gas ambient by scanning tunneling microscopy

We investigated the cleaning process of Si(1 0 0) surfaces by annealing in H₂ gas ambient following chemical treatments by scanning tunneling microscopy. We observed the monohydride Si structure: Si(1 0 0):2 × 1-H on the surfaces annealed at 1000 °C in 2.5 × 10⁴ Pa H₂ gas ambient without conspicuous contaminants. On the sample annealed for 10 min or longer times, well-defined Si(1 0 0) structures with alternating S_A and S_B steps were observed, whereas the initial roughness still remained on the surfaces annealed for only 5 min.     

PLD of X7R for thin film capacitors

Thin film capacitors with a thickness of 200 nm were prepared on SrTiO₃ (1 0 0), (1 1 0) and (1 1 1) single crystal substrates at a temperature of 973 K by pulsed laser deposition (PLD) using a KrF excimer laser in an O₂-O₃ atmosphere with a gas pressure of 1 Pa using an X7R sintered target. As a result, perovskite BaTiO₃ solid solution films were obtained. In the X7R thin films on (1 0 0) and (1 1 0) SrTiO₃, only diffraction peaks with strong intensities from BaTiO₃ (1 0 0) and (1 1 0), respectively, were observed. X7R films on SrTiO₃ (1 1 1) were grown epitaxially oriented to the crystal plane direction of the substrate by inserting an initial homoepitaxial SrTiO₃ layer with a thickness of 4 nm. The X7R/SrTiO₃ film capacitors yielded a large volumetric efficiency of 50 μF/mm³ and a temperature coefficient of capacitance (TCC) of −1.3% to 1.3% which satisfies the EIA standard specifications for X7R.     

Annealing effects on structural, optical and electrical properties of e-beam evaporated CuIn0.5Ga0.5Te2 thin films

CuIn_0.5Ga_0.5Te₂ (CIGT) thin films have been prepared by e-beam evaporation from a single crystal powder synthesized by direct reaction of constituent elements in a stoichiometric proportion. Post-depositional annealing has been carried out at 300 and 350 °C. The compositions of the films were determined by energy dispersive X-ray analysis (EDXA) and it was found that there was a remarkable fluctuation in atomic percentage of the constituent elements following to the post-depositional annealing. X-ray diffraction analysis (XRD) has shown that as-grown films were amorphous in nature and turned into polycrystalline structure following to the annealing at 300 °C. The main peaks of CuIn_0.5Ga_0.5Te₂ and some minor peaks belonged to a binary phase Cu₂Te appeared after annealing at 300 °C, whereas for the films annealed at 350 °C single phase of the CuIn_0.5Ga_0.5Te₂ chalcopyrite structure was observed with the preferred orientation along the (1 1 2) plane. The effect of annealing on and near surface regions has been studied using X-ray photoelectron spectroscopy (XPS). The results indicated that there was a considerable variation in surface composition following to the annealing process. The transmission and reflection measurements have been carried out in the wavelength range of 200-1100 nm. The absorption coefficients of the films were found to be in the order of 10⁴ cm⁻¹ and optical band gaps were determined as 1.39, 1.43 and 1.47 eV for as-grown and films annealed at 300 and 350 °C, respectively. The temperature dependent conductivity and photoconductivity measurements have been performed in the temperature range of −73 to 157 °C and the room temperature resistivities were found to be around 3.4 × 10⁷ and 9.6 × 10⁶ (Ω cm) for the as-grown and annealed films at 350 °C, respectively.     

Influence of epitaxial growth on phase competition in Pr0.5Sr0.5MnO3 films

A series of Pr_0.5Sr_0.5MnO₃ (PSMO) films with various thickness were epitaxially grown on substrates of (0 0 1)-oriented (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (LSAT), LaAlO₃ (LAO) and SrTiO₃ (STO), and (0 1 1)-oriented STO using pulse laser deposition. Influence of epitaxial growth on phase competition was investigated. A ferromagnetic metal to antiferromagnetic insulator (FMM-AFI) transition upon cooling is present in both largely compressed situations deposited on LAO (0 0 1) and tensile cases deposited on STO (0 0 1) but absent in little strained films grown on LSAT (0 0 1), indicating that the antiferromagnetic insulating state is favored by strains. On the other hand, the 400 nm films deposited on (0 1 1)-oriented STO as well as LAO substrates show FMM-AFI transition. These results reveal that both the orientation of epitaxial growth and substrate-induced strain affect the FMM-AFI transition.     

Thin film substrates from the Raman spectroscopy point of view

We have investigated ten standard single crystal substrates of complex oxides on the account of their applicability in the Raman spectroscopy‐based thin film research. In this study, we suggest a spectra normalization procedure that utilizes a comparison of the substrate's Raman spectra to those of well‐established Raman reference materials. We demonstrate that MgO, LaGaO₃, (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.7 (LSAT), DyScO₃, YAlO₃, and LaAlO₃ can be of potential use for Raman‐based thin film research. At the same time TiO₂ (rutile), NdGaO₃, SrLaAlO₄, and SrTiO₃ single crystals exhibit multiple phonon modes accompanied by strong Raman background that substantially hinder Raman‐based thin film experiments. Copyright © 2014 John Wiley & Sons, Ltd.