Investigation of BiFeO3 Multiferroic thin films prepared by metalloorganic chemical vapor deposition

BiFeO₃ thin oriented films are grown on SrTiO₃(001) and ZrO₂(Y₂O₃)(001) substrates by metalloorganic chemical vapor deposition (MOCVD) in the temperature range T= 500–800°C. Iron dipivaloylmethanate Fe(thd)₃ and triphenylbismuth Bi(C₆H₅)₃ are used as volatile precursors. It is shown that the high thermal stability of Bi(C₆H₅)₃ leads to significant deviations of the Bi: Fe ratio in the film from their ratio in the precursor flow. An increase in the residence time of the precursor flow in the reactor makes this ratio close to unity. The film-substrate epitaxial relations are determined. It is found that the film orientation on the ZrO₂(Y₂O₃)(001) substrate changes with increasing temperature. Optical second harmonic generation (SHG) measurements show the presence of ferroelectric ordering in the films. A significant decrease in the Curie temperature due to epitaxial stress is found. At the same time, the magnetization noticeably increases as compared to a BiFeO₃ single crystal.     

Polar properties of hydrothermally synthesized BiFeO3 thin films

Multiferroic bismuth ferrite (BiFeO₃) has attracted considerable attention due to applications related to the bulk photovoltaic effect in which the direction of polarization determines the direction of the photocurrent. Epitaxial thin films are produced by means of techniques that usually require high temperature processes. The hydrothermal method can be seen as an alternative route to obtain highly textured thin films in quantities compatible with batch processing; nevertheless, the structural, dielectric and electric properties are generally affected by the presence of hydrogen and other reaction by-products. In this work, functional and highly textured BiFeO₃ films were successfully produced on metallic SrTiO₃:Nb (0.5 wt.%) (100) substrates via hydrothermal synthesis. X-ray diffraction (XRD) and Atomic Force Microscopy (AFM) were used to analyze the structural properties of the films. Piezoresponse Force Microscopy (PFM) and Photoconductive Atomic Force Microscopy (Pc-AFM) were used to determine their functional properties. We show the polarization switching and confirm the presence of the bulk photovoltaic effect for the first time in hydrothermally synthesized BiFeO₃.     

Structure and composition of silicon carbide films synthesized by ion implantation

The mathematical decomposition of the IR absorption spectrum obtained from a Si layer after the C⁺ ion implantation with an energy of 10 or 40 keV or from a homogeneous SiC_0.7 film has demonstrated that fractions of weak elongated Si-C bonds in the amorphous phase, strong shortened Si-C bonds on the surface of small nanocrystals, and tetrahedral Si-C bonds in the crystalline phase (degree of crystallinity) after high-temperature annealing (1250–1400°C) of the layers are equal to 29/29/42, 22/7/71, and 21/31/48%, respectively. A system of SiC_2.0, SiO₂, SiC_0.8, and SiC_0.6 layers in the film on the Si substrate has been identified using X-ray reflectometry and the simulation with the Release software. The reflectometry data on fluctuations of the intensity of X-ray reflections in the region of the main maximum have been interpreted in terms of variations in the density over the depth of the layer with a Gaussian distribution of carbon atoms from 2.55 and 2.90 g/cm³ for the SiC_0.25 and SiC_0.65 layers, respectively, to 3.29 g/cm³ for the SiC_1.36 layer.     

Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

Improvement of fatigue resistance on La modified BiFeO3 thin films

The effect of lanthanum (La) addition in BiFeO₃ (BFO) thin films deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates prepared by soft chemical method was explained. Increasing La concentration promotes changes on structure, microstructure and dielectric/ferroelectric response of films. X-ray diffraction reveals that the films are free of preferred orientations and structural distortion. La addition promotes an increase in dielectric permittivity. The polarization switching and the fatigue behavior of the BFO films were significantly enhanced by the La concentration.     

Multiferroic phase transition near room temperature in BiFeO3 films

In multiferroic BiFeO(3) thin films grown on highly mismatched LaAlO(3) substrates, we reveal the coexistence of two differently distorted polymorphs that leads to striking features in the temperature dependence of the structural and multiferroic properties. Notably, the highly distorted phase quasiconcomitantly presents an abrupt structural change, transforms from a standard to a nonconventional ferroelectric, and transitions from antiferromagnetic to paramagnetic at 360±20 K. These coupled ferroic transitions just above room temperature hold promises of giant piezoelectric, magnetoelectric, and piezomagnetic responses, with potential in many applications fields.     

Optical and dielectric properties of PVA capped nanocrystalline PbS thin films synthesized by chemical bath deposition

Nanoparticles of lead sulfide (PbS) have been grown within the pores of polyvinyl alcohol (PVA) matrix on glass substrates by chemical bath deposition at and below room temperature (30 °C). Lead acetate and thiourea, dissolved in an alkaline medium, were taken as the sources of lead and sulfur. X-ray diffraction and selected area electron diffraction studies confirmed the cubic nanocrystalline PbS phase formation. Transmission electron micrograph of the films revealed the particle size lying in the range 10–20 nm. X-ray photoelectron spectroscopic studies confirmed the presence of lead and sulfur in the films, and their atomic ratios were found to be dependent on the deposition temperature. UV–vis spectrophotometric measurement showed a direct allowed band gap lying in the range 2.40–2.81 eV, which is much higher than the bulk value (0.41 eV). The band gap decreases with the increase of deposition temperature. The dielectric constant of the PVA-capped nanocrystalline PbS was in the range 155–265 at higher frequencies, which is much higher compared to only PVA and bulk PbS.     

Photovoltaic effect in BiFeO3/BaTiO3 multilayer structure fabricated by chemical solution deposition technique

Photovoltaic (PV) properties of bismuth ferrite (BFO) and barium titanate (BTO) multilayered ferroelectric BFO/BTO/BFO/BTO thin film structure deposited on Pt/Ti/SiO₂/Si substrates using chemical solution deposition technique are presented. X-ray diffraction analysis confirms pure phase polycrystalline nature of deposited perovskite multilayered structures. Simultaneously both distorted rhombohedral (R3c) and tetragonal phases (P4mm) of the respective BFO and BTO components are also well retained. The ferroelectric sandwiched structures grown on fused quartz substrates exhibit high optical transmittance (~70%) with an energy band gap 2.62 eV. Current–voltage characteristics and PV response of multilayered structures is determined in metal-ferroelectric-metal (MFM) capacitor configuration. Considerably low magnitude of dark current density 1.53×10⁻⁷ A at applied bias of 5 V establish the resistive nature of semi-transparent multilayered structure. Enhanced PV response with 40 nm thin semitransparent Au as top electrode is observed under solid-state violet laser illumination (λ – 405 nm, 160 mW/cm²). The short circuit current density and open circuit voltage are measured to be 12.65 µA/cm² and 1.43 V respectively with a high retentivity. The results obtained are highly encouraging for employing artificial multilayered engineering to improve PV characteristics.     

Magnetic properties of BiFeO3 micro-cubes synthesized by microwave agitation

In this article, we present results of field cooled (FC) and zero field cooled (ZFC) magnetization measurements and investigation of aging and memory effect in bismuth ferrite (BFO) multiferroic micro-cubes obtained by means of simple microwave synthesis procedure. It is found that difference between FC and ZFC magnetizations appear at the temperature of freezing of ferromagnetic domain walls. The decay of the magnetic moment versus time described by power-law relation and the absence of memory effect are caused by domain growth mechanism rather than by the spin-glass phase. The negligible value of remnant magnetic moment indicates that BFO compound exhibits low concentration of ferromagnetic domains and can be close to ferromagnetic to spin-glass transition.     

BiFeO3 thin films: Novel effects

In this paper we report synthesis of phase-pure highly resistive magnetoelectric BiFeO₃ thin films on Pt/TiO₂/SiO₂/Si substrate by using pulsed laser deposition technique. For the first time saturated ferroelectric hysteresis loop has been observed. It has confirmed the presence of ferroelectricity in BiFeO₃ compound. The films exhibit dielectric anomaly near Neel temperature. This anomaly is related to the influence of vanishing magnetic order on the electric order. In situ domain alignment occurs during observation of the films under transmission electron microscope.     

Structure and phase composition of thin a-C:H films modified by Ag and Ti

The structure and phase composition of thin a-C:H and a-C:H〈M〉 films (M = Ag, Ti, or Ag + Ti) have been studied by Raman and X-ray photoelectron spectroscopy. The a-C:H〈M〉 films were prepared by ion-plasma magnetron sputtering of a combined target of graphite and metal in an Ar–CH₄ gas mixture. The Raman spectra of these films indicate that their structure is amorphous. The a-C:H〈Ag + Ti〉 films have a more graphitized structure in comparison with pure a-C:H films and films containing only one metal. It is established that carbon in the a-C:H〈Ag + Ti〉 films is in the sp ², sp ³, and C=O states, which are characteristic of the a-C:H, a-C:H〈Ag〉, and a-C:H〈Ti〉 films. In addition, there are also ether (–C–O–C–) or epoxy (?C?O–) carbon groups in the a-C:H〈Ag + Ti〉 films. It has been revealed that silver atoms in the a-C:H〈Ag〉 and a-C:H〈Ag + Ti〉 films form no chemical bonds with carbon, oxygen, and titanium. Titanium in the a-C:H〈Ti〉 and a-C:H〈Ag + Ti〉 films exists in the form of titanium IV oxide (TiO₂).     

Structure and hardness of a-C:H films prepared by middle frequency plasma chemical vapor deposition

a-C:H films were prepared by middle frequency plasma chemical vapor deposition (MF-PCVD) on silicon substrates from two hydrocarbon source gases, CH₄ and a mixture of C₂H₂ + H₂, at varying bias voltage amplitudes. Raman spectroscopy shows that the structure of the a-C:H films deposited from these two precursors is different. For the films deposited from CH₄, the G peak position around 1520 cm⁻¹ and the small intensity ratio of D peak to G peak (I(D)/I(G)) indicate that the C-C sp³ fraction in this film is about 20 at.%. These films are diamond-like a-C:H films. For the films deposited from C₂H₂ + H₂, the Raman results indicate that their structure is close to graphite-like amorphous carbon. The hardness and elastic modulus of the films deposited from CH₄ increase with increasing bias voltage, while a decrease of hardness and elastic modulus of the films deposited from a mixture of C₂H₂ + H₂ with increasing bias voltage is observed.     

Structure of Ba0.7Sr0.3TiO3 films grown by chemical solution deposition on polycor substrates

The structure of barium strontium titanate (BST) films grown by chemical solution deposition on polycor substrates was studied by transmission electron microscopy, high-resolution microscopy, and x-ray diffraction analysis. It was found that a grain structure inhomogeneous in cross section is formed after two-step crystallization at T = 700 and 950°C. There are equiaxed grains (44.2 nm in average size) in the BST-polycor interfacial region and a multilevel columnar structure (grain height up to 150 nm) with {100} texture in the film bulk. Grain growth inhibition during high-temperature annealing and underlayer formation in the interfacial region are caused by a change in the substrate structure, i.e., grain reorientation and {112} texture formation.     

Thermal stability of ultrathin amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition and filtered cathodic vacuum arc

Abstract

Ultrathin hydrogenated amorphous carbon (a-C:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and hydrogen-free amorphous carbon (a-C) films of similar thickness deposited by filtered cathodic vacuum arc (FCVA) were subjected to rapid thermal annealing (RTA). Cross-sectional transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to study the structural stability of the films. While RTA increased the thickness of the intermixing layer and decreased the sp³ content of the a-C:H films, it did not affect the thickness or the sp³ content of the a-C films. The superior structural stability of the FCVA a-C films compared with PECVD a-C:H films, demonstrated by the TEM and EELS results of this study, illustrates the high potential of these films as protective overcoats in applications where rapid heating is critical to the device functionality and performance, such as heat-assisted magnetic recording.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

ZnO films grown by successive chemical solution deposition

ZnO films were grown from 0.1-M zincate solutions on stainless-steel and aluminosilicate glass substrates by the successive chemical solution deposition method. The structure, morphology, composition, and optical emission properties of the films were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and photoluminescence techniques. Results revealed that the as-grown film contains a substantial amount of amorphous zinc hydroxide (15–25%), at least on its surface. This can be reduced to 7% by annealing the film in argon (350 °C, 1 h). Despite the presence of the hydroxide phase, the films hexagonal lattice constants match the standard values. The films surface texture and the grains shape and preferential orientation depend on the type of the substrate and its surface conditioning. The UV photoluminescence emission from as-grown films at 3.22±0.04 eV (380–390 nm) and its suppression due to the effect of chlorine are addressed. PACS 81.16.Be; 81.05.Dz; 78.55.Et; 79.60.-i; 68.55.Jk     

Structure of (Ba0.7Sr0.3)TiO3 films prepared by chemical solution deposition on sapphire substrates

Barium strontium titanate (BST) films on single-crystal sapphire substrates are prepared by chemical solution deposition upon annealing at temperatures T = 700, 850, and 1000°C. The structure of the BST films is investigated using transmission electron microscopy, high-resolution electron microscopy, and x-ray diffraction. It is established that, upon annealing at T = 700 and 850°C, the film crystallizes in the tetragonal phase of the (Ba_0.7Sr_0.3)TiO₃ perovskite without texture and transition layers. The mean grain sizes are 17 and 37 nm, respectively. However, an increase in the annealing temperature to 1000°C brings about a decrease in the mean grain size to 25 nm and the appearance of additional phases due to the interaction at the film-substrate interface.     

Electric field driven phase transition and possible twining quasi-tetragonal phase in compressively strained BiFeO3 thin films

Highly compressively strained BiFeO₃ thin films with different thickness are epitaxially grown on (001) LaAlO₃ substrates and characterized using various techniques. The quasi-tetragonal phase with a giant axial ratio of ?? 1.25 and its thickness-dependent evolution are investigated. An interesting twining structure of the quasi-tetragonal phase is evidenced in thicker films through detailed reciprocal space mapping, which becomes more pronounced with increasing film thickness. Moreover, an interesting electric-field driven phase transition was evidenced in the film with a thickness of 38 nm, in which the quasi-tetragonal and rhombohedral phases are close to each other in energy landscape.     

Growth of polycrystalline La0.5Sr0.5CoO3 films by femtosecond pulsed laser deposition

In this paper we present the growth of La_0.5Sr_0.5CoO₃ (LSCO) films on MgO, quartz, and silicon substrates by pulsed laser deposition (PLD) using a Ti:sapphire laser (50 fs, 800 nm wavelength). The morphology and the structure of the films were studied by X-ray diffraction, atomic force microscopy, and scanning electron microscopy. The films were polycrystalline and exhibit a good adherence to the Si substrate. Different deposition parameters such as substrate temperature, oxygen pressure, and laser fluence were varied to achieve good surface quality and low resistivity crystalline films. We also defined the optimum conditions in which the deposited film surface is particulate free. The best films (droplets free) were grown at 625 °C, in an ambient oxygen pressure of 6 mbar, with an incident laser fluence of 0.19 J/cm². This is a mandatory step in the complex work of fabricating La_0.5Sr_0.5CoO₃/BaTiO₃/La_0.5Sr_0.5CoO₃ heterostructures for the development of thin film capacitors for non-volatile ferroelectric access memory devices. PACS 81.15 Fg; 42.62-b; 68.65.Ac