Electrodiffusion phenomena in C<Subscript>60</Subscript> thin films

As part of our ongoing research program to produce semiconductor devices based on C₆₀ thin films, we report here on our first attempts at the intercalative doping of C₆₀ thin films through the diffusion of metals. Two techniques were employed: (a) chemically induced counter electrodiffusion of Cu and I₂ into a C₆₀ matrix and (b) Au diffusion under the action of an external electric field.     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

X-ray spectral analysis of the interface of a thin Al<Subscript>2</Subscript>O<Subscript>3</Subscript> film prepared on silicon by atomic layer deposition

The extent and phase chemical composition of the interface forming under atomic layer deposition (ALD) of a 6-nm-thick Al₂O₃ film on the surface of crystalline silicon (c-Si) has been studied by depthresolved, ultrasoft x-ray emission spectroscopy. ALD is shown to produce a layer of mixed Al₂O₃ and SiO₂ oxides about 6–8 nm thick, in which silicon dioxide is present even on the sample surface and its concentration increases as one approaches the interface with the substrate. It is assumed that such a complex structure of the layer is the result of interdiffusion of oxygen into the layer and of silicon from the substrate to the surface over grain boundaries of polycrystalline Al₂O₃, followed by silicon oxidation. Neither the formation of clusters of metallic aluminum near the boundary with c-Si nor aluminum diffusion into the substrate was revealed. It was established that ALD-deposited Al₂O₃ layers with a thickness up to 60 nm have similar structure.     

Thermally stimulated desorption of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes from rigid-chain polyimide films

Polyimide-fullerene composite thin coatings are investigated using thermal desorption mass spectrometry in the temperature range 20–800°C. It is found that, at temperatures below the temperature of decom-position of the polymer matrix, thermally stimulated desorption of fullerene molecules is limited by the diffusion of fullerene molecules in the matrix. The diffusion coefficients and activation energies of diffusion of C₆₀ and C₇₀ fullerene molecules are determined from the experimental data on thermally stimulated desorption in the framework of several approaches. It is revealed that the diffusion of C₇₀ molecules in the polyimide matrix is more hindered than the diffusion of C₆₀ molecules in the same matrix.     

Preferential growth of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> films with a nanolayer structure: enhancement of thermoelectric properties induced by nanocrystal boundaries

Preferential growth of different crystal planes in layered Bi₂Te₃ thin films with each layer <40 nm has been achieved by a simple magnetron co-sputtering method. The preferential growth of (015) plane or (001) was achieved at special depositing conditions due to the more sufficient growth along the in-plane direction induced by the enhanced diffusion of atoms and lower deposition rate. The Bi₂Te₃ film with preferential growth of (001) plane possesses about two times higher electrical conductivity and Seebeck coefficient as compared to the film with preferential growth of (015) plane, due to the greatly enhanced carrier mobility. Furthermore, the thermal conductivity has been suppressed due to more phonon scattering at grain boundaries, compared with ordinary Bi₂Te₃ alloys and films.     

Processing of C<Subscript>60</Subscript> thin films by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

Thin films of fullerenes (C₆₀) were deposited onto silicon using matrix-assisted pulsed laser evaporation (MAPLE). The deposition was carried out from a frozen homogeneous dilute solution of C₆₀ in anisole (0.67 wt%), and over a broad range of laser fluences, from 0.15 J/cm² up to 3.9 J/cm². MAPLE has been applied for deposition of fullerenes for the first time and we have studied the growth of thin films of solid C₆₀. The fragmentation of C₆₀ fullerene molecules induced by ns ablation in vacuum of a frozen anisole target with C₆₀ was investigated by matrix-assisted laser desorption/ionization (MALDI). Our findings show that intact fullerene films can be produced with laser fluences ranging from 0.15 J/cm² up to 1.5 J/cm².     

Electrical and Optical Properties of Cu<Subscript>2</Subscript>Zn(Fe,Mn)SnS<Subscript>4</Subscript> Films Prepared by Spray Pyrolysis

We have analyzed the electrical and optical properties of Cu₂ZnSnS₄, Cu₂FeSnS₄, and Cu₂MnSnS₄ films with the p-type electrical conductivity, which were prepared by spray pyrolysis at temperature TS = 290°C using 0.1 M aqueous solutions of salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, MnCl₂ · 2H₂O, FeCl₃ · 6H₂O, SnCl₄ · 5H₂O, and (NH₂)CS. The energy parameters have been determined from analyzing the electrophysical properties of the films using the model of energy barriers at grain boundaries in polycrystalline materials, and the thickness of intercrystallite boundaries has been estimated. The extent of the influence of the hole concentration p₀ in the bulk of crystallites and height E _b of the energy barriers between grains on the electrical conductivity has been determined. The optical bandgap width for thin Cu₂Zn(Fe,Mn)SnS₄ films has been calculated based on analyzing the spectral dependences of the absorption coefficient.     

Effect of electron irradiation on the physicochemical processes in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6+<Emphasis Type="Italic">x</Emphasis></Subscript> high-temperature ceramics

The influence of irradiation by 2-MeV electrons at integral doses of 0.1, 0.3, 1.5, and 3.0 MGy on the physicochemical processes in YBa₂Cu₃O_6+x polycrystalline samples is investigated. At different stages of irradiation, processes occurring in the samples exert an opposing effect on the matrix and near-surface regions of the material. Irradiation with doses D<1.5 MGy strengthens bonds in the intergranular spacer, which weaken because of a reduction in the potential surface barrier for oxygen migration to vacant sites. This results in ordering of the oxygen sublattice in near-surface regions. Irradiation with doses D>1.5 MGy causes damage on the grain surface, which enhances oxygen diffusion from the bulk and, thus, leads to material degradation.     

Optical properties and mechanisms of current flow in Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.     

Crystallographic orientation dependence of the dielectric constant in polymorphic BaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> thin films deposited by laser ablation

Well-crystallized barium metaniobate (BaNb₂O₆) thin films were fabricated on fused quartz substrates by pulsed laser deposition. The influence of substrate temperature and oxygen pressure on the crystal structure and preferred orientation were studied to understand the growth mechanism of BaNb₂O₆ thin films. The films formed at 600 °C at an oxygen pressure of 100 mTorr exhibited predominantly the orthorhombic (040) orientation, and turned to the orthorhombic (230) orientation at 800 °C. It was found that (220)-oriented hexagonal thin films were formed at 600 °C at an oxygen pressure less than 50 mTorr. The dielectric constant of the BaNb₂O₆ thin films was measured by scanning microwave microscopy (SMM). Preferentially (230)-oriented orthorhombic and (220)-oriented hexagonal BaNb₂O₆ thin films were shown to have significantly enhanced dielectric constants of 47.8 and 56.7, respectively. This could be attributed to the dependence of the dielectric constant on crystallographic orientation. PACS 77.55.+f; 77.84.Dy     

Phase transition behavior of highly (100) textured sol-gel-derived Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> thin films

We have investigated the relations between microstructure and dielectric properties in order to fabricate sol-gel-derived highly (100) oriented Ba_0.5Sr_0.5TiO₃ (BST 50/50) thin films with properties comparable to those of the bulk material. For the first time, we were able to fabricate BST thin films which exhibited the orthorhombic-to-tetragonal transition in addition to the commonly observed tetragonal-to-cubic transition. We were successful in explaining the commonly observed degradation of the dielectric behavior of BST thin films, when compared to that of the bulk material, in terms of grain size, compositional inhomogeneity (measured in terms of Sr/Ba ratio) between the grain bulk and grain boundary, and mechanical stresses. PACS 77.55.+f; 77.22Gm; 77.80.Bh; 77.80.Dj     

Epitaxial growth of C<Subscript>60</Subscript> thin films on the Bi(0001)/Si(111) surface

The morphology and atomic structure of C₆₀ fullerene films on the Bi(0001)/Si(111)?7 × 7 surface with different coverages have been studied by scanning tunneling microscopy and spectroscopy and low-energy electron microscopy in high vacuum. It is shown that the most favorable sites for nucleation of C₆₀ islands are double steps and domain boundaries on the surface of epitaxial Bi film.     

Growth of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> films on the Si(111) surface covered by a thin SiO<Subscript>2</Subscript> layer

Magnetite polycrystalline films are grown by variously oxidizing a Fe film on the Si(111) surface covered by a thin (1.5 nm) SiO₂ layer. It is found that defects in the SiO₂ layer influence silicidation under heating of the Fe film. The high-temperature oxidation of the Fe film results in the formation of both Fe₃O₄ and iron monosilicide. However, the high-temperature deposition of Fe in an oxygen atmosphere leads to the growth of a compositionally uniform Fe₃O₄ film on the SiO₂ surface. It is found that such a synthesis method causes [311] texture to arise in the magnetite film, with the texture axis normal to the surface. The influence of the synthesis method on the magnetic properties of grown Fe₃O₄ films is studied. A high coercive force of Fe₃O₃ films grown by Fe film oxidation is related to their specific morphology and compositional nonuniformity.     

Absorption Spectra of C<Subscript>60</Subscript> Fullerene Monomolecular Films

The absorption spectra of C₆₀ fullerene thin (from submonolayer to 5–6 monolayers) films deposited on different substrates have been studied. It has been shown that the spectra of the submonolayer and thick (more than 100 monolayers) films virtually coincide. The behavior of fullerene on the surface of different polymers can be judged from changes in the absorption spectra.     

The structure of fullerite C<Subscript>60</Subscript> intercalated with molecular oxygen

A (O₂) _x C₆₀ sample with a high content of oxygen (x ≥ 0.4) and free of technological solvent impurities was obtained by precipitation from solution. For the first time, the results of the determination of the x coefficients using ¹³C NMR and elemental analysis were compared. It was shown by Raman spectroscopy, mass spectrometry, and NMR that the inclusion of oxygen into fullerite was accompanied by a decrease in the frequency of O=O stretching vibrations by no less than 12 cm⁻¹ compared with gaseous O₂. Nevertheless, oxygen exists in the molecular form in (O₂)_0.4C₆₀ and is released in the form of O₂ as the sample is heated to 373 K. The number of oxygen molecules occupying octahedral pores closets to the fullerene molecule takes on all the possible values, from 0 to 6. At room temperature, the (O₂) _x C₆₀ sample lost oxygen much more slowly than similar products prepared by diffusion saturation of pure fullerite with oxygen.     

Micro-Raman spectroscopic investigation of NiSi films formed on BF<Subscript>2</Subscript><Superscript>+</Superscript>-, B<Superscript>+</Superscript>- and non-implanted (100)Si substrates

The micro-Raman spectroscopic technique was used to investigate vibrational properties of NiSi thin films formed on three different (100)Si substrates: non-implanted, 20 keV BF₂⁺-implanted, and 20 keV B⁺-implanted. Raman measurements were also performed on NiSi powder to identify various phonon modes associated with different selection rules of group theory. It was found that the Raman peaks for NiSi thin films formed on the BF₂⁺-implanted substrate were broader and shifted to lower frequencies compared to those for films formed on the other substrates. The broadening of the Raman peaks for these films, which also exhibit much improved thermal stability, is attributed to the small grains that probably result from the segregation of fluorine to grain boundaries and interfaces. It is further proposed that grain boundary segregation influences the stress in the silicide film, resulting in shifts in phonon peak positions. PACS 78.30.Am; 74.25.Kc; 68.35.Dv; 68.55.Ln; 66.30.Jt     

Electric and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> bilayer thin films prepared by pulsed-laser deposition

CoFe₂O₄ (CFO) thin film with highly (111)-preferential orientation was first deposited on the silicon substrate by a pulsed-laser deposition, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) layers were deposited with different oxygen pressures to form the bilayer CFO/PZT nanocomposite thin films. X-ray diffraction showed that the PZT preferential orientation was strongly dependant on the oxygen pressure. The smooth film surface was obtained after depositing the CFO and PZT layers. The bilayer thin films exhibit good ferromagnetic and ferroelectric properties, and a low leakage current density of 0.004 μA/cm² at 50 kV/cm. The leakage current density curves show loops for the electric polarized field when the electric field reverses. PACS 77.84.Lf; 75.80+q; 81.05.Zx; 81.15.Fg     

Mechanism of grain-boundary magnetoresistance in Fe O films

The magnetotransport properties of magnetite films with different microstructures were investigated in order to identify prerequisites for the attainment of a large tunnelling magnetoresistance in polycrystalline samples. Epitaxial films on MgAl₂O₄, polycrystalline films on Al₂O₃ and rough MgAl₂O₄ substrates and a polycrystalline La_0.7Ca_0.3MnO₃ film on MgO were compared. Although grain boundaries induce a large high-field magnetoresistance in magnetite films, the low-field magnetoresistance characteristic for spin-polarized tunnelling was virtually absent in these samples. Two factors might be responsible for this behaviour: (1) grain boundaries in magnetite are conducting and do not form tunnelling barriers and (2) the spin-polarization near grain boundaries is suppressed due to non-stoichiometry. Received 15 April 2002 Published online 13 August 2002     

Local leakage current behaviours of BiFeO3 films

The leakage current behaviours of polycrystalline BiFeO₃ thin films are investigated by using both conductive atomic force microscopy and current-voltage characteristic measurements. The local charge transport pathways are found to be located mainly at the grain boundaries of the films. The leakage current density can be tuned by changing the post-annealing temperature, the annealing time, the bias voltage and the light illumination, which can be used to improve the performances of the ferroelectric devices based on the BiFeO₃ films. A possible leakage mechanism is proposed to interpret the charge transports in the polycrystalline BiFeO₃ films.