Grain Boundary Diffusion in C<Subscript>60</Subscript> Thin Films

This paper focuses on the effect of grain boundaries on the diffusion processes in polycrystalline C₆₀ thin films. Electrically induced diffusion of Au was investigated by in situ measurements of the film conductivity. Electron Paramagnetic Resonance (EPR) spectroscopy was used to study diffusion of oxygen. Increase in grain sizes in polycrystalline C₆₀ thin films was found to result in the acceleration of gold and oxygen diffusion. The results are interpreted assuming that these impurities diffuse in C₆₀ films dominantly along grain boundaries.     

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.     

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.     

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.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Study of third-and fifth-order nonlinear optical processes in thin C<Subscript>60</Subscript> films

The nonlinear refraction in thin films of fullerene C₆₀ (100 nm) is studied by the Z-and RZ-scan methods using the second harmonic of a picosecond Nd:YAG laser (λ = 532 nm, τ = 55 ps). The combined effect of n₂ (self-focusing of laser radiation) and n₄ (self-defocusing) is analyzed. Mechanisms responsible for the nonlinear refraction in films are discussed.     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Photopolymerization of C<Subscript>60</Subscript> and Li@C<Subscript>60</Subscript> studied by second-harmonic generation and infrared spectroscopy

The photopolymerization of C₆₀ and Li@C₆₀ films was investigated by means of optical second-harmonic generation. The films were deposited under ultra-high-vacuum conditions and irradiated in situ with an Ar⁺ laser at 514 nm. The second harmonic generated by a Nd:YAG laser working at 1064 nm was monitored after different steps of irradiation. Photopolymerization was observed after very low irradiation doses, of the order of 10²⁰ photons/cm², and confirmed with infrared absorption spectroscopy. Similar kinetics for C₆₀ and Li@C₆₀ were observed. The measurements give evidence for photopolymerization of the endohedral fullerene Li@C₆₀. PACS 78.30.Na; 82.50.Hp; 81.05.Tp     

Effect of deposition time on structural and physical properties of Cu<Subscript>2</Subscript>CdSnS<Subscript>4</Subscript> thin films prepared by spray pyrolysis technique: experimental and ab initio study

Cu₂CdSnS₄ (CCdTS) thin films were synthesized using chemical spray pyrolysis deposition technique. The effect of various deposition times (20, 40, 60 min) on growth of these films was investigated. The as-synthesized Cu₂CdSnS₄ thin films were characterized by X-ray diffraction (XRD), ultraviolet–visible (UV–Vis) spectroscopy, Raman spectroscopy and Hall Effect measurements. The XRD pattern of Cu₂CdSnS₄ structured in stannite phase with preferential orientations along (112) planes. Raman spectrum revealed very strong peak at about 333 cm^?1. The films have the direct optical band gaps of 1.39–1.5 eV. The optimum hole mobility was found to be 3.212 × 10¹ cm² v^?1 s^?1 for the film deposited on 60 min. The electronic structure and optical properties of the stannite structure Cu₂CdSnS₄ were obtained by ab initio calculations using the Korringa–Kohn–Rostoker method combined with the Coherent Potential Approximation (CPA), as well as CPA confirms our results.     

On the interaction of self-assembled C<Subscript>60</Subscript>F<Subscript>18</Subscript> polar molecules with the Ni(100) surface

The current work is dedicated to investigation of the interaction between self-assembled polar molecules of fullerene fluoride C₆₀F₁₈ with the chemically active surface Ni(100) under radiation and heat treatments. X-ray photoelectron spectroscopy is used in combination with quantum-chemical simulation. For the first time, the transformation of an as-deposited dielectric continuous 2D thin film to a 3D island-type assembly with molecular ordering within the islands is shown to take place. The degree of coverage of the Ni surface by C₆₀F₁₈ islands (0.6–0.7) and their height (~6 nm) are estimated. Quantum-chemical simulation shows that the chemisorption energy of the C₆₀F₁₈ molecule on the Ni surface equals ~6.6 eV and fluorine atoms are located at a distance of 1.9 Å above the Ni surface. The results of the investigation provide an opportunity to create nanoscale ordered structures with local changes in the work function.     

Coercive field enhancement in microstructured (La<Subscript>0.4</Subscript>Pr<Subscript>0.6</Subscript>)<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> thin films

The perovskite material (La_0.4Pr_0.6)_0.67Ca_0.33MnO₃ (LPCMO) has complex electronic and magnetic behavior based on phase competition between ferromagnetic metallic (FMM) and insulating phases with similar free energies. Experimental evidence has indicated that in-plane stress anisotropy influences these phases and can affect electronic and magnetic properties. Here we investigate the roles that both stress and shape anisotropies may play in controlling the coercive field of the material. LPCMO thin films of various thicknesses (20, 25, and 30 nm) were deposited on (110) NdGaO₃ (NGO) substrates using pulsed laser deposition and the coercive fields were measured. Photolithography was then used to fabricate microstructured arrays of LPCMO on the NGO substrates for each of the films. The coercive fields of these arrays of LPCMO were compared to the behavior of the corresponding unpatterned LPCMO thin films across a range of temperatures. Microstructure arrays for the thicker (25 and 30 nm) films showed a substantial increase in the coercive field after forming the arrays, whereas a thinner film (20 nm) showed almost no change in the coercive field. Stress anisotropy continues to play a dominant role in the behavior of LPCMO thin films and dimensionality of the magnetic domains also influences the results. The films show 2D behavior when film thickness approaches the size of the critical radius for single-to-multidomain transitions. Making thicker films allows for 3D behavior and a role for shape anisotropy to influence the coercive fields.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Fabrication of a thin film containing C<Subscript>60</Subscript> derivative nanodomains by photo- polymerization of diacetylene acid

A simple approach for preparing a thin film containing C₆₀ derivative (C₆₀-COOH) nanodomains, based on the mixed Langmuir–Blodgett (LB) film of C₆₀-COOH and diacetylene acid (DA), is reported. From the observations of atomic force microscopy, it is found that many small domains in the mixed LB film are formed, which differ from the flat film of pure C₆₀-COOH. Upon the photopolymerization of DA molecules in the mixed LB film, these nanodomains become much smaller and more homogeneous in size and distribution. PACS 68.37.Ps; 68.18.-g; 64.70.Nd; 68.47.Pe; 68.55.-a     

Effect of substitution of vanadium on the structure and electrical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

The ferroelectric and dielectric properties of Bi_4-xLa_xTi₃O₁₂ (BLT) and Bi_4-xLa_xTi_2.97V_0.03O₁₂ (BLTV) thin films deposited on (111)Pt/Ti/SiO₂/Si substrates using a chemical solution method were investigated. The BLTV thin films showed a larger remanent polarization (9.6 C/cm²) than the BLT thin films (6.5 C/cm²), while the coercive field for both thin films was nearly the same. The capacitance of the films as a function of a small ac driving field was measured, and the data were processed using Rayleighs law. The results show that the Rayleigh constant of the BLT films was smaller than that of the BLTV films, indicating that the defect concentration was lower in the latter case. The superior ferroelectricity of the BLTV films was attributed to a decrease of both the (001) orientation and the defect concentration. PACS 77.80.Bh; 77.55.+f     

Molecular dynamics study of orientational melting and thermodynamic properties of C<Subscript>60</Subscript>@C<Subscript>240</Subscript> nanoparticles

The barriers to relative shell rotation and other energy characteristics of C₆₀@C₂₄₀ two-shell carbon nanoparticles (“onions”) with outer shells of different shapes are calculated. The disturbance of the orientational order in the mutual arrangement of shells with an increase in temperature (orientational melting) is studied by the molecular dynamics method. The intershell orientational diffusion is represented by the Arrhenius relationship, and the Arrhenius parameters are calculated numerically. A definition is proposed for the temperature of short-range order disturbance in systems that undergo melting without structural change. The calculated temperature of orientational melting of the C₆₀@C₂₄₀ nanoparticle is approximately equal to 60 K.     

Response of the electrical resistivity and magnetoresistance of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films to biaxial compressive mechanical (001) or (110) strains

The behavior of the electrical resistivity and magnetoresistance of 40-to 120-nm-thick La_0.67Ca_0.33MnO₃ films grown on differently oriented lanthanum aluminate substrates was studied. The cell volume in thin (40 nm) La_0.67Ca_0.33MnO₃ films grown coherently on (001)LaAlO₃ was found to be substantially smaller. Mechanical stress relaxation in biaxially strained La_0.67Ca_0.33MnO₃ films is accompanied by an increase in the cell volume. The temperatures at which the electrical resistivity and magnetoresistance in biaxially strained La_0.67Ca_0.33MnO₃ films were maximum can differ by 60–70 K from those observed in bulk single crystals.     

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     

Rapid optical measurement of surface roughness of BiFeO<Subscript>3</Subscript> films for nonvolatile memory application

An optical inspection system for rapid surface roughness measurement of BiFeO₃ (BFO) thin films is developed. It is found that y = −121.45 x + 212.81 is a trend equation for characterizing the surface roughness of BFO thin films. The incident angle of 60◦ is a good candidate for measuring the surface roughness of BFO thin films. The maximum measurement error rate of the optical inspection system developed is less than 2.6%. The savings in inspection time of the surface roughness of BiFeO₃ thin films is up to 90%.     

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     

Effects of BaTiO<Subscript>3</Subscript> and SrTiO<Subscript>3</Subscript> as the buffer layers of epitaxial BiFeO<Subscript>3</Subscript> thin films

BiFeO₃ (BFO) thin films with BaTiO₃ (BTO) or SrTiO₃ (STO) as buffer layer were epitaxially grown on SrRuO₃-covered SrTiO₃ substrates. X-ray diffraction measurements show that the BTO buffer causes tensile strain in the BFO films, whereas the STO buffer causes compressive strain. Different ferroelectric domain structures caused by these two strain statuses are revealed by piezoelectric force microscopy. Electrical and magnetical measurements show that the tensile-strained BFO/BTO samples have reduced leakage current and large ferroelectric polarization and magnetization, compared with compressively strained BFO/STO. These results demonstrate that the electrical and magnetical properties of BFO thin films can be artificially modified by using a buffer layer.