Polyethylene terephthalate (PET) bulk film analysis using C60, Au3, and Au primary ion beams

The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C₆₀⁺, Au₃⁺ and Au⁺ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]⁺ is on average 5× higher for C₆₀⁺ than Au₃⁺ and 8× higher for Au₃⁺ than Au⁺. Damage accumulates under Au⁺ and Au₃⁺ bombardment while C₆₀⁺ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of ∼1 × 10¹⁵ ions cm⁻². These properties of C₆₀⁺ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.     

Substrate effects on the analysis of biomolecular layers using Au, Au3 and C60 bombardments

Effects of platinum silicon, graphite and PET substrates on the secondary ion yield of sub-monolayer and multilayer samples of Cyclosporin A following 20 keV Au⁺, Au₃⁺and C₆₀⁺ impacts have been investigated. The obtained results of sub-monolayer samples show that platinum enhances the yield of the pseudo-molecular ion following Au⁺ and Au₃⁺ impacts due to the high density of the substrate that enables the energy of the primary ions to be deposited near the surface. C₆₀⁺ impacts on sub-monolayer samples are less effective, but there is an enhancement on PET substrates. Impacts of 20 keV Au⁺ and Au₃⁺ are not very efficient on multilayer samples. 20 keV C₆₀⁺ impacts enhance the yields significantly, especially for the relatively high molecular weight [M+H]⁺ ion.     

The effect of C60 cluster ion beam bombardment in sputter depth profiling of organic-inorganic hybrid multiple thin films

The effects of C₆₀ cluster ion beam bombardment in sputter depth profiling of inorganic-organic hybrid multiple nm thin films were studied. The dependence of SIMS depth profiles on sputter ion species such as 500 eV Cs⁺, 10 keV C₆₀⁺, 20 keV C₆₀²⁺ and 30 keV C₆₀³⁺ was investigated to study the effect of cluster ion bombardment on depth resolution, sputtering yield, damage accumulation, and sampling depth.     

Correlation between Al2O3 particles and interface of Al-Al2O3 coatings by cold spray

Al-Al₂O₃ composite coatings with different Al₂O₃ particle shapes were prepared on Si and Al substrate by cold spray. The powder compositions of metal (Al) and ceramic (Al₂O₃) having different sizes and agglomerations were varied into ratios of 10:1 wt% and 1:1 wt%. Al₂O₃ particles were successfully incorporated into the soft metal matrix of Al. It was found that crater formation between the coatings and substrate, which is typical characteristic signature of cold spray could be affected by initial starting Al₂O₃ particles. In addition, when the large hard particles of fused Al₂O₃ were employed, the deep and big craters were generated at the interface between coatings and hard substrates. In the case of pure soft metal coating such as Al on hard substrate, it is very hard to get proper adhesion due to lack of crater formation. Therefore, the composite coating would have certain advantages.     

The effect of incident angle on the C60 bombardment of molecular solids

The effect of incident angle on the quality of SIMS molecular depth profiling using C₆₀⁺ was investigated. Cholesterol films of ∼300 nm thickness on Si were employed as a model and were eroded using 40 keV C₆₀⁺ at an incident angle of 40° and 73° with respect to the surface normal. The erosion process was characterized by determining at each angle the relative amount of chemical damage, the total sputtering yield of cholesterol molecules, and the interface width between the film and the Si substrate. The results show that there is less molecule damage at an angle of incidence of 73° and that the total sputtering yield is largest at an angle of incidence of 40°. The measurements suggest reduced damage is not necessarily dependent upon enhanced yields and that depositing the incident energy nearer the surface by using glancing angles is most important. The interface width parameter supports this idea by indicating that at the 73° incident angle, C₆₀⁺ produces a smaller altered layer depth. Overall, the results show that 73° incidence is the better angle for molecular depth profiling using 40 keV C₆₀⁺.     

Magnetotransport properties of epitaxial Pr0.5Ca0.5MnO3 films grown by a solution technique

Epitaxial Pr_0.5Ca_0.5MnO₃ films have been synthesized on (0 0 1) SrTiO₃ substrate using a chemical solution deposition technique and two-step post-annealing process. The zero field resistivity of the films shows semiconducting behavior and a characteristic of charge ordering is observed at 230 K. The resistivity of the 10 nm film did not show any effect with the magnetic field. However, melting of charge ordering was observed for the 120 nm film at an applied magnetic field of 4 T. Large decrease in the resistivity of the 120 nm film (<100 K) resulted in magnetoresistance of nearly −100% at 75 K.     

Sputtering yields of PMMA films bombarded by keV C60 ions

A quartz crystal microbalance (QCM) has been used to determine total-mass sputtering yields of PMMA films by 1-16 keV C₆₀^+,2+ ion beams. Quantitative sputtering yields for PMMA are presented as mass loss per incident ion Y_m. Mass-lost rate QCM data show that a 13 keV C₆₀ cluster leads to emission equivalent to 800 PMMA molecules per ion. The power law obtained for the increase in sputtering yield with primary ion energy is in good agreement those predicted by “thermal spike” regime and MD models, when crater sizes are used to estimate sputtering.     

Structural characterization of La0.9Ba0.1MnO3/Y-ZrO2 film by X-ray diffraction

Perovskite manganite La_0.9Ba_0.1MnO₃(LBMO) films were deposited on (0 0 1)-oriented single crystal yttria-stabilized zirconia (YSZ) substrate by 90° off-axis radio frequency magnetron sputtering. The film thickness ranged from 10 nm to 100 nm. Grazing incidence X-ray diffraction technique and high resolution X-ray diffraction were applied to characterize the structure of LBMO films. The LBMO film mainly consisted of (0 0 1)-orientated grain as well as weakly textured (1 1 0)-orientated grain. The results indicated that an amorphous layer with thickness of about 4 nm was formed at the LBMO/YSZ interface. The strain in LBMO film was small and averaged to be about -0.14%. The strain in the film was not lattice mismatch-induced strain but residual strain due to the difference in thermal expansion coefficient between film and substrate.     

Comparative study of optical parameters of fullerene C60 film at different temperatures

Fullerene C₆₀ thin films on glass substrate (around 2000 ? thickness) were prepared by thermal evaporation technique. The structural, surface morphology and optical properties of the films were studied. The optical properties of fullerene C₆₀ were investigated in the spectral range 200 nm to 900 nm using a UV-Vis spectrophotometer at room temperature as well as at liquid nitrogen temperature (77 K). The optical band gap at room temperature is found to be 2.30 eV, which gradually decreases with lowering the temperature and reaches to 2.27 at 77 K. The thickness and refractive index of fullerene C₆₀ film were calculated by ellipsometry. From the X-ray analysis, we have calculated the grain size, dislocation density, number of crystallite per unit area, and strain of the film at room temperature. The surface morphology of film was analyzed by scanning electron microscope (SEM). The present result show that the fullerene C₆₀ film becomes more conducting at low temperature.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Effects of deposition parameters on laser-induced damage threshold of Ta2O5 films

Ta₂O₅ films were deposited on BK7 substrates by e-beam evaporation with different deposition parameters such as substrate temperature (323-623 K), oxygen pressure (0.5-3.0×10⁻² Pa) and deposition rate (0.2-0.5 nm/s). Absorption, scattering and chemical composition were investigated by surface thermal lensing (STL) technique, total integrated scattering (TIS) measurement and X-ray photoelectron spectroscopy (XPS), respectively. The laser-induced damage threshold (LIDT) was assessed using pulsed Nd:YAG 1064 nm laser at a pulse length of 12 ns. The results showed that optical properties, absorption and LIDT were influenced by the deposition parameters and annealing. However, scattering was little correlated with the deposition parameters. On the whole, the LIDT increased with increasing substrate temperature and oxygen pressure, whereas it increased firstly and then decreased upon increasing deposition rate. After annealing at 673 K for 12 h, the LIDT of films improved significantly. The dependence of possible damage mechanism on deposition parameters was discussed.     

Photon-assisted synthesis of C60 polymers by laser irradiation

The harmonics of a free electron laser (FEL) were irradiated in vacuum to surfaces of compressed C₆₀ and a mixture of C₆₀ and I₂. The power and frequency of the fundamental FEL macro-pulse were ca. 0.5 mJ/pulse and 2 Hz, respectively. The irradiation time was 120-180 min. After irradiation of FEL with a typical wavelength of 450 or 345 nm, the Raman peak of Ag(2)-derived vibration mode of C₆₀ shifted to the lower-energy side. The Raman peak shift of the mixture powder sample was greater than that of pure C₆₀. Furthermore, changes of the crystalline structure indicated that various intermolecular combinations occurred by irradiation. These results strongly suggest that three-dimensional polymerization of C₆₀ was promoted by laser irradiation and the effect of photon-assisted hole-doping from iodine atoms to C₆₀ molecules.     

Formation of Sim and SimCn clusters by C60 sputtering of Si

The secondary ion mass spectrum of silicon sputtered by high energy C₆₀⁺ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Si_m⁺ (1 ≤ m ≤ 15) and various Si_mC_n⁺ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Si_m⁺ clusters up to Si₇⁺ are significant (between 0.1 and 0.6 of the Si⁺ yield) with even numbered clusters Si₄⁺ and Si₆⁺ having the highest probability of formation. The abundances of cluster ions between Si₈⁺ and Si₁₁⁺ are still significant (>1% relative to Si⁺) but drop by a factor of ∼100 between Si₁₁⁺ and Si₁₃⁺. The probability of formation of clusters Si₁₃⁺-Si₁₅⁺ is approximately constant at ∼5 × 10⁻⁴ relative to Si⁺ and rising a little for Si₁₅⁺, but clusters beyond Si₁₅ are not detected (Si_m≥16⁺/Si⁺ < 1 × 10⁻⁴). The probability of formation of Si_m⁺ and Si_mC_n⁺ clusters depends only very weakly on the C₆₀⁺ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Si_m⁺ and Si_mC_n⁺ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C₆₀⁺ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Si_m⁺ clusters produced during C₆₀⁺ sputtering of silica (SiO₂) and various silicate minerals. The abundances for clusters heavier than Si₂⁺ are very small compared to the case where Si is the target.The data reported here suggest that Si_m⁺ and Si_mC_n⁺ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.     

Stretching the limits of static SIMS with C60

Pristine and Au-covered molecular films have been analyzed by ToF-SIMS (TRIFT™), using 15 keV Ga⁺ (FEI) and 15 keV C₆₀⁺ (Ionoptika) primary ion sources. The use of C₆₀⁺ leads to an enormous yield enhancement for gold clusters, especially when the amount of gold is low (2 nmol/cm²), i.e. a situation of relatively small nanoparticles well separated in space. It also allows us to extend significantly the traditional mass range of static SIMS. Under 15 keV C₆₀⁺ ion bombardment, a series of clusters up to a mass of about 20,000 Da (Au₁₀₀⁻: 19,700 Da) is detected. This large yield increase is attributed to the hydrocarbon matrix (low-atomic mass), because the yield increase observed for thick metallic films (Ag, Au) is much lower. The additional yield enhancement factors provided by the Au metallization procedure for organic ions (MetA-SIMS) have been measured under C₆₀⁺ bombardment. They reach a factor of 2 for the molecular ion and almost an order of magnitude for Irganox fragments such as C₄H₉⁺, C₁₅H₂₃O⁺ and C₁₆H₂₃O⁻.     

An XPS study and electrical properties of Pb1.1Zr0.53Ti0.47O3/PbO/Si (MFIS) structures according to the substrate temperature of the PbO buffer layer

PbO and PZT thin films were deposited on the p-type (1 0 0) Si substrate by the rf magnetron sputtering method with PbO and Pb_1.1Zr_0.53Ti_0.47O₃ targets for the application of the metal-ferroelectric-insulator-semiconductor (MFIS) structure. The MFIS structures with the PbO buffer layer show the good electric properties including a high memory window and a low leakage current density. The maximum value of the memory window is 2.0 V under the applied voltage of 9 V for the Pt/PZT (200 nm, 400 °C)/PbO (80 nm)/Si structures with the PbO buffer layer deposited at the substrate temperature of 300 °C. From the X-ray photoelectron spectroscopy (XPS) results, we could confirm that the substrate temperature of PbO affects the chemical states of the interface between the PbO buffer layer and Si substrate, which results in the inter-diffusion of Pb and the formation of the intermediate phases (PbSiO₃). And the existence of the undesired SiO₂ layer, which is the low dielectric layer, was confirmed at the surface region of the Si substrate by the XPS depth profile analysis.     

Optical limiting action of C60 doped poly(dimethylacetylendicarboxylate)

The optical limiting action of poly(dimethylacetylendicarboxylate) polymer doped with fullerene C₆₀ has been investigated under irradiation with 10 ns laser pulses at 532 nm. The optical limiting measurements were performed at four different dopant concentrations. The threshold limiting fluence at 0.3 J/cm² was observed at high doping concentrations, with transmission of about 55%. An explanation based on the combination of two-photon absorption and reverse saturable absorption was proposed for its nonlinear optical absorption behavior.     

Artifacts in the sputtering of inorganics by C60

In the present study, the basic issues in C₆₀ⁿ⁺ sputtering are studied using silicon, gold and platinum samples. Sputtering yields are measured for energies in the range of 5-30 keV, by sputtering micrometre sized craters on the surface of flat clean samples and measuring their volumes using atomic force microscopy (AFM). Net deposition of carbon occurs for all three materials at 5 keV, and is not specific to silicon which forms a carbide. The threshold energy for net sputtering is dependent on the sputtering yield and the stopping power of the substrate. Away from the threshold, the sputtering yields agree well with Sigmund and Claussen's thermal spike model after allowance for the sputtering of the deposited carbon atoms. AFM images show the formation of unusual surface topography around the transition region between sputtering and deposition. Analysis of the bottom of a crater using imaging SIMS shows a significant enhancement of carbon clusters as well as various silicon-carbon groups, indicating the importance of carbon deposition and implantation in a gradual mixed layer formed from sputtering. The thickness of this interface layer is shown to be approximately 5 nm.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

A detailed chemical kinetic model for oxidation of C₂H₄ in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C₂H₃ + O₂ reaction was used to obtain rate coefficients over a wide range of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar and medium temperatures vinyl peroxide, rather than CH₂O and HCO, is the dominant product. The experiments, involving C₂H₄/O₂ mixtures diluted in N₂, were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C₂H₄ are more complex than those prevailing at higher temperatures and lower pressures. The major differences are the importance of the hydroxyethyl (CH₂CH₂OH) and 2-hydroperoxyethyl (CH₂CH₂OOH) radicals, formed from addition of OH and HO₂ to C₂H₄, and vinyl peroxide, formed from C₂H₃ + O₂. Hydroxyethyl is oxidized through the peroxide HOCH₂CH₂OO (lean conditions) or through ethenol (low O₂ concentration), while 2-hydroperoxyethyl is converted through oxirane.     

Optical limiting behavior of C60 doped ethylenepropylenediene polymethylene polymer

Optical limiting measurements on C₆₀ in toluene-ethylenepropylenediene polymethylene (EPDM) polymer blends and in EPDM polymer films at three different concentrations have been carried out. The measurements were undertaken using 532 nm wavelength, 10 ns pulses from a frequency-doubled Nd-YAG Laser. The results show that the optical limiting efficiency is concentration dependent and that the limiting efficiency for C₆₀ in toluene-EPDM polymer blends is better than in EPDM polymer film samples.