Investigation of molecular weight effects of polystyrene in ToF-SIMS using C60 and Au primary ion beams

In secondary ion mass spectrometry, polyatomic primary ion sources are known to enhance yields from many surfaces including polymers. In order to understand the fundamental causes for these increases, the enhancement as a function of material type and molecular weight needs to be delineated. In this article, we report results from a systematic investigation of polymeric films of polystyrene (PS) with varying molecular weights to examine the influence of the primary ion beam on the secondary ion yields in time of flight secondary ion mass spectrometry (ToF-SIMS). The masses of the polymers investigated ranged from 1000 to 20,000 Da, or from about n = 10 to 200 where n indicates the number of polymeric units in a polymer chain. The polymers had a narrow molecular weight range (PDI < 1.07). The multilayer polymeric films (10-30 nm) characterized by AFM were prepared by spin-casting onto silicon substrates and were analyzed using Au⁺ and C₆₀⁺ primary ion beams. The analysis with the two beams provided a useful comparison between atomic and polyatomic primary ion sources. Information gathered from this study provides insight into the role of molecular weight on the observed yield enhancement from polyatomic ion sources.     

Depth profiling of cells and tissues by using C60 and SF5 as sputter ions

In the present study, SF₅⁺ and C₆₀⁺ were used as primary ions for sputtering and Bi₃⁺ was used as primary ions for analysis. The depth profiling procedure was utilized to make 3D images of the chemistry of single cultured cells and tissue samples of intact intestinal epithelium.The results show sputtering of organic material from cells and tissue with both SF₅⁺ and C₆₀⁺ sources. Cholesterol fragments were found in the superficial layers when sputtering with C₆₀⁺. Spectra were collected revealing the change in yield along the z-axis of the sample. 3D images of the localization of Na, K, phosphocholine and cholesterol were constructed with both ion sources for single cell cultures and the mouse intestine.Cryostate sections of mouse intestine were analysed in 2D and the results were compared with the 3D image of the intestine. The localization of cholesterol and phosphocholine was found to be similar in cryostate sections analysed in two dimensions and the sputtered, freeze-dried intestine analysed in 3D. The comparison of 2D and 3D images suggest that the phosphocholine signal faded with C₆₀⁺ sputtering. In conclusion, both C₆₀⁺ and SF₅⁺ can be used as primary ion sources for sputtering of organic material from cells and tissues. Consecutive analysis with a Bi₃⁺ source can be used to obtain image stacks that could be used for reconstruction of 3D images.     

Bombardment induced surface chemistry on Si under keV C60 impact

Molecular dynamics simulations of the sputtering of Si by C₆₀ keV bombardment are performed in order to understand the importance of chemical reactions between C atoms from the projectile and Si atoms in the target crystal. The simulations predict the formation of strong covalent bonds between the C and Si atoms, which result in nearly all of the C atoms remaining embedded in the surface after bombardment. At low incident kinetic energies, little sputtering of Si atoms is observed and there is a net deposition of solid material. As the incident kinetic energy is increased, the sputtering yield of Si atoms increases. At 15 keV, the yield of sputtered Si atoms is more than twice the number of C atoms deposited, and there is a net erosion of the solid material.     

Simulations of C60 bombardment of Si, SiC, diamond and graphite

Molecular dynamics simulations of the 20-keV C₆₀ bombardment at normal incidence of Si, SiC, diamond and graphite targets were performed. The unique feature of these targets is that strong covalent bonds can be formed between carbon atoms from the C₆₀ projectile and atoms in the solid material. The mesoscale energy deposition footprint (MEDF) model is used to gain physical insight into how the sputtering yields depend on the substrate characteristics. A large proportion of the carbon atoms from the C₆₀ projectile are implanted into the lattice structure of the target. The sputtering yield from SiC is ∼twice that from either diamond or Si and this can be explained by both the region of the energized cylindrical tract created by the impact and the number density. On graphite, the yield of sputtered atoms is negligible because the open lattice allows the cluster to deposit its energy deep within the solid. The simulations suggest that build up of carbon with a graphite-like structure would reduce any sputtering from a solid with C₆₀⁺ bombardment.     

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.     

Controlling energy deposition during the C60 bombardment of silicon: The effect of incident angle geometry

The profile of the energy deposition footprint is controlled during the C₆₀⁺ erosion of Si surfaces by varying the incident energy and/or incident angle geometry. Sputter yield, surface topography, and chemical composition of the eroded surfaces were characterized using atomic force microscopy (AFM) and secondary ion mass spectrometry (SIMS). The experiments show that the 10 keV, 40° incident C₆₀⁺ erosion of Si results in the formation of a C containing, mound-like structure on the solid surface. We find that the occurrence of this C feature can be avoided by increasing the incident energy of the C₆₀⁺ projectile or by increasing the incident angle of the C₆₀⁺ projectile. While both strategies allow for the Si samples to be eroded, the occurrence of topographical roughening limits the usefulness of C₆₀⁺ in ultra-high resolution semiconductor depth profiling. Moreover, we find that the relative effect of changing the incident angle geometry of the C₆₀⁺ projectile on the profile of the energy deposition footprint, and thus the sputter yield, changes according to the kinetic energy of the projectile and the material of the bombarded surface, a behavior that is quite different than what is observed for an atomic counterpart.     

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⁺.     

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⁻.     

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.     

Energy distributions of atomic and molecular ions sputtered by C60 projectiles

In the process of investigating the interaction of fullerene projectiles with adsorbed organic layers, we measured the kinetic energy distributions (KEDs) of fragment and parent ions sputtered from an overlayer of polystyrene (PS) oligomers cast on silver under 15 keV C₆₀⁺ bombardment. These measurements have been conducted using our TRIFT™ spectrometer, recently equipped with the C₆₀⁺ source developed by Ionoptika, Ltd. For atomic ions, the intensity corresponding to the high energy tail decreases in the following order: C⁺(E^−0.4) > H⁺(E^−1.5) > Ag⁺(E^−3.5). In particular, the distribution of Ag⁺ is not broader than those of Ag₂⁺ and Ag₃⁺ clusters, in sharp contrast with 15 keV Ga⁺ bombardment. On the other hand, molecular ions (fragments and parent-like species) exhibit a significantly wider distribution using C₆₀⁺ instead of Ga⁺ as primary ions. For instance, the KED of Ag-cationized PS oligomers resembles that of Ag⁺ and Ag_n⁺ clusters. A specific feature of fullerene projectiles is that they induce the direct desorption of positively charged oligomers, without the need of a cationizing metal atom. The energy spectrum of these PS⁺ ions is significantly narrower then that of Ag-cationized oligomers. For characteristic fragments of PS, such as C₇H₇⁺ and C₁₅H₁₃⁺ and polycyclic fragments, such as C₉H₇⁺ and C₁₄H₁₀⁺, the high energy decay is steep (E⁻⁴ − E⁻⁸). In addition, reorganized ions generally show more pronounced high energy tails than characteristic ions, similar to the case of monoatomic ion bombardment. This observation is consistent with the higher excitation energy needed for their formation. Finally, the fraction of hydrocarbon ions formed in the gas phase via unimolecular dissociation of larger species is slightly larger with gallium than with fullerene projectiles.     

C60 sputtering of organics: A study using TOF-SIMS, XPS and nanoindentation

Sputtering of organic materials using a C₆₀ primary ion beam has been demonstrated to produce significantly less accumulated damage compared to sputtering with monatomic and atomic-cluster ion beams. However, much about the dynamics of C₆₀ sputtering remains to be understood. We introduce data regarding the dynamics of C₆₀ sputtering by evaluating TOF-SIMS depth profiles of bulk poly(methyl methacrylate) (PMMA). Bulk PMMA provides an ideal test matrix with which to probe C₆₀ sputter dynamics because there is a region of steady-state secondary ion yield followed by irreversible signal degradation. C₆₀ sputtering of PMMA is evaluated as a function of incident ion kinetic energy using 10 keV C₆₀⁺, 20 keV C₆₀⁺ and 40 keV C₆₀⁺⁺ primary ions. Changes in PMMA chemistry, carbon accumulation and graphitization, and topography as a function of total C₆₀ ion dose at each accelerating potential is addressed.     

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.     

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.     

Sputtering of amorphous ice induced by C60 and Au3 clusters

Molecular dynamics simulations were performed to study the behavior of cluster SIMS. Two predominant cluster ion beam sources, C₆₀ and Au₃, were chosen for comparison. An amorphous water ice substrate was bombarded with incident energy of 5 keV. The C₆₀ cluster was observed to shatter upon impact creating a crater of damage approximately 8 nm deep. Although Au₃ was also found to both break apart and form a damage crater, it continued along its initial trajectory causing damage roughly 10 nm deep into the sample and becoming completely imbedded. It is suggested that this difference in behavior is due to the large mass of Au relative to the substrate water molecule.     

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.     

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.     

Intermolecular photoinduced electron-transfer processes between C60 and aniline derivatives in benzonitrile

The quenching behavior of the triplets of C₆₀ by various aniline derivatives (1a-d and 2a-e) was investigated by means of laser flash photolysis in benzonitrile at 293 K. Electron transfer process was proposed to be the main mechanism because of the direct detection of radical ions of aniline derivatives and C₆₀ in time-resolved transient absorption spectra. The quenching rate constants (k_q) of by different substrates determined at 740 nm approach or reach the diffusion-controlled limit. DFT method was employed to calculate the unknown oxidation potentials of substrates in solution. With these E_ox values, free energy changes (ΔG) were obtained through Rehm-Weller equation. Dependence of observed quenching rate constants on the free energy changes further indicates the photoinduced reactions between ³C₆₀^* and substrates proceed through an electron transfer mechanism. Obtained k_q values for the aniline derivatives are impacted obviously by ground-state configurations and the kinds substituents quantified by Hammett σ constant. Good correlation between log k_q and σ values conforms to the empirical Hammett equation. A more negative ρ value (−3.356) was gained for anilines (2a-e) than that of N,N-dimethylanilines (1a-d) (−1.382), which suggests a more susceptible reactivity for the former substrates. Charge density distribution of reaction center “N” originated from quantum calculation supports this suggestion. In addition, a relationship between quenching rate constants and solvent viscosity was gained from C₆₀/dimethyl-p-toluidine system in altered mixtures of acetonitrile and toluene.     

Solvent-induced optical properties of C60

Different C₆₀ aggregates, i.e. nanoparticles, clusters of nanoparticles and microcrystals in room-temperature solutions, are reported to account for the colors of fluorescence emissions centered at 440, 575 and 700 nm, respectively. And the configurations of C₆₀ aggregation created in solutions are revealed to be closely associated with the characteristic interactions between C₆₀ and solvent molecules. On this basis, aggregation behaviors and thus induced optical properties of C₆₀ have been tentatively controlled through adopting solvent mixtures.     

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.     

Transport properties and mechanism of C60 coupled to carbon nanotube electrode

By applying non-equilibrium Green's functions in combination with density-functional theory, we investigate electronic transport properties of C₆₀ coupled to carbon nanotubes and Li electrodes. The results show that electronic transport properties of CNT-C₆₀-CNT and Li-C₆₀-Li systems are completely different. Nonlinear I-V characteristic, varistor-type behavior and negative differential resistance (NDR) phenomenon are observed when electrodes are carbon nanotubes. We discuss the mechanism of I-V characteristics of CNT-C₆₀-CNT systems in details. Our results suggest conductance, energy level of Frontier molecular orbitals, energy gap between HOMO and LUMO, the coupling between molecular orbitals and electrodes are all playing critical roles in electronic transport properties.