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 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.     

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.     

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.     

Fundamental studies of the cluster ion bombardment of water ice

The fundamental sputtering properties of water ice are of interest for molecular depth profiling of biological samples in their native environment. We report on a method of studying amorphous water ice films of precise thicknesses in which pure water vapor is condensed onto a pre-cooled, silver-coated quartz crystal microbalance (QCM). This scheme allows for the determination of water ice sputter yields for any primary projectile as well as providing a means for studying escape depths of atoms and molecules beneath the deposited water ice layer. Specifically, we find a removal of approximately 2500 water molecule equivalents/20 keV C₆₀⁺ projectile with an underlying silver ion escape depth of 7.0 Å.     

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.     

Model multilayer structures for three-dimensional cell imaging

The prospects for SIMS three-dimensional analysis of biological materials were explored using model multilayer structures. The samples were analyzed in a ToF-SIMS spectrometer equipped with a 20 keV buckminsterfullerene (C₆₀⁺) ion source. Molecular depth information was acquired using a C₆₀⁺ ion beam to etch through the multilayer structures at specified time intervals. Subsequent to each individual erosion cycle, static SIMS spectra were recorded using a pulsed C₆₀⁺ ion probe. Molecular intensities in sequential mass spectra were monitored as a function of primary ion fluence. The resulting depth information was used to characterize C₆₀⁺ bombardment of biological materials. Specifically, molecular depth profile studies involving dehydrated dipalmitoyl-phosphatidylcholine (DPPC) organic films indicate that cell membrane lipid materials do not experience significant chemical damage when bombarded with C₆₀⁺ ion fluences greater than 10¹⁵ ions/cm². Moreover, depth profile analyses of DPPC-sucrose frozen multilayer structures suggest that biomolecule information can be uncovered after the C₆₀⁺ sputter removal of a 20 nm overlayer with no appreciable loss of underlying molecular signal. The experimental results support the potential for three-dimensional molecular mapping of biological materials using cluster SIMS.     

Cluster SIMS using metal cluster complex ions

Metal cluster complexes are chemically synthesized organometallic compounds, which have a wide range of chemical compositions with high molecular weight. Using a metal cluster complex ion source, sputtering characteristics of silicon bombarded with normally incident Ir₄(CO)₇⁺ ions were investigated. Experimental results showed that the sputtering yield at 10 keV was 36, which is higher than that with Ar⁺ ions by a factor of 24. In addition, secondary ion mass spectrometry (SIMS) of boron-delta-doped silicon samples and organic films of poly(methyl methacrylate) (PMMA) was performed. Compared with conventional O₂⁺ ion beams, Ir₄(CO)₇⁺ ion beams improved depth resolution by a factor of 2.5 at the same irradiation conditions; the highest depth resolution of 0.9 nm was obtained at 5 keV, 45° with oxygen flooding of 1.3 × 10⁻⁴ Pa. Furthermore, it was confirmed that Ir₄(CO)₇⁺ ion beams significantly enhanced secondary ion intensity in high-mass region.     

Ion sputtering rates of W-, Ti- and Cr-carbides studied at different Ar ion incidence angles

To study the ion sputtering rates of W-, Ti- and Cr-carbides, trilayer structures comprising C-graphite (59 nm)/WC (50 nm)/W (38 nm), C-graphite (56 nm)/TiC (40 nm)/Ti (34 nm) and C-graphite (46 nm)/C₃C₂ (60 nm)/Cr (69 nm) with a tolerance ±2% were sputter deposited onto smooth silicon substrates. Their precise structural and compositional characterization by transmission electron microscopy (TEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) revealed that the WC and Cr₃C₂ layers were amorphous, while the TiC layer had a polycrystalline structure. The ion sputtering rates of all three carbides, amorphous carbon and polycrystalline Cr, Ti and W layers were determined by means of Auger electron spectroscopy depth profiling as a function of the angle of incidence of two symmetrically inclined 1 keV Ar⁺ ion beams in the range between 22° and 82°. The sputtering rates were calculated from the known thicknesses of the layers and the sputtering times necessary to remove the individual layers. It was found that the sputtering rates of carbides, C-graphite and metals were strongly angle dependent. For the carbides in the range between 36° and 62° the highest ion sputtering rate was found for Cr₃C₂ and the lowest for TiC, while the values of the sputtering rates for WC were intermediate. The normalized sputtering yields calculated from the experimentally obtained data for all three carbides followed the trend of theoretical results obtained by calculation of the transport of ions in solids by the SRIM code. The sputtering yields are also presented in terms of atoms/ion. Our experimental data for two ion incidence angles of 22° and 49° and reported values of other authors for C-graphite and metals are mainly inside the estimated error of about ±20%. The influence of the ion-induced surface topography on the measured sputtering yields was estimated from the atomic force microscope (AFM) measurements at the intermediate points of the corresponding layers on the crater walls formed during depth profiling.     

Molecular depth profiling of multi-layer systems with cluster ion sources

Cluster bombardment of molecular films has created new opportunities for SIMS research. To more quantitatively examine the interaction of cluster beams with organic materials, we have developed a reproducible platform consisting of a well-defined sugar film (trehalose) doped with peptides. Molecular depth profiles have been acquired with these systems using C₆₀⁺ bombardment. In this study, we utilize this platform to determine the feasibility of examining buried interfaces for multi-layer systems. Using C₆₀⁺ at 20 keV, several systems have been tested including Al/trehalose/Si, Al/trehalose/Al/Si, Ag/trehalose/Si and ice/trehalose/Si. The results show that there can be interactions between the layers during the bombardment process that prevent a simple interpretation of the depth profile. We find so far that the best results are obtained when the mass of the overlayer atoms is less than or nearly equal to the mass of the atoms in buried molecules. In general, these observations suggest that C₆₀⁺ bombardment can be successfully applied to interface characterization of multi-layer systems if the systems are carefully chosen.     

Depth profiling using C60 SIMS—Deposition and topography development during bombardment of silicon

A C₆₀⁺ primary ion source has been coupled to an ion microscope secondary ion mass spectrometry (SIMS) instrument to examine sputtering of silicon with an emphasis on possible application of C₆₀⁺ depth profiling for high depth resolution SIMS analysis of silicon semiconductor materials. Unexpectedly, C₆₀⁺ SIMS depth profiling of silicon was found to be complicated by the deposition of an amorphous carbon layer which buries the silicon substrate. Sputtering of the silicon was observed only at the highest accessible beam energies (14.5 keV impact) or by using oxygen backfilling. C₆₀⁺ SIMS depth profiling of As delta-doped test samples at 14.5 keV demonstrated a substantial (factor of 5) degradation in depth resolution compared to Cs⁺ SIMS depth profiling. This degradation is thought to result from the formation of an unusual platelet-like grain structure on the SIMS crater bottoms. Other unusual topographical features were also observed on silicon substrates after high primary ion dose C₆₀⁺ bombardment.     

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.     

Structural effects of C60 bombardment on various natural mineral samples—Application to analysis of organic phases in geological samples

Organic phases trapped inside natural mineral samples are of considerable interest in astrobiology, geochemistry and geobiology. Examples of such organic phases are microfossils, kerogen and oil. Information about these phases is usually retrieved through bulk crushing of the rock which means both a risk of contamination and that the composition and spatial distribution of the organics to its host mineral is lost. An attractive of way to retrieve information about the organics in the rock is depth profiling using a focused ion beam. Recently, it was shown that it is possible to obtain detailed mass spectrometric information from oil-bearing fluid inclusions, i.e. small amounts of oil trapped inside a mineral matrix, using ToF-SIMS. Using a 10 keV C₆₀⁺ sputter beam and a 25 keV Bi₃⁺ analysis beam, oil-bearing inclusions in different minerals were opened and analysed individually. However, sputtering with a C₆₀⁺ beam also induced other changes to the mineral surface, such as formation of topographic features and carbon deposition. In this paper, the cause of these changes is explored and the consequences of the sputter-induced features on the analysis of organic phases in natural mineral samples (quartz, calcite and fluorite) in general and fluid inclusions in particular are discussed.The dominating topographical features that were observed when a several micrometers deep crater is sputtered with 10 keV C₆₀⁺ ions on a natural mineral surface are conical-shaped and ridge-like structures that may rise several micrometers, pointing in the direction of the incident C₆₀⁺ ion beam, on an otherwise flat crater bottom. The sputter-induced structures were found to appear at places with different chemistry than the host mineral, including other minerals phases and fluid inclusions, while structural defects in the host material, such as polishing marks or scratches, did not necessarily result in sputter-induced structures. The ridge-like structures were often covered by a thick layer of deposited carbon.Despite the appearance of the sputter-induced structures and carbon deposition, most oil-bearing inclusions could successfully be opened and analysed. However, smaller inclusion (<15 μm) could potentially become entirely covered by sputter-resistant structures and therefore difficult to open. Therefore, it might become necessary, to for example increase the ion energy and rotate the stage to successfully open smaller inclusions for analysis.SIMS, C₆₀, carbon deposition, topography, mineral, fluid inclusions, geological samples, depth profiling.     

Analysis of C60 and Cs sputtering ions for depth profiling gold/silicon and GaAs multilayer samples by time of flight secondary ion mass spectrometry

Time of flight secondary ion mass spectrometry (ToF-SIMS) depth profiles of several inorganic layered samples using Cs⁺ and C₆₀⁺ primary sputtering ions of different energies are compared to evaluate sputter yield and depth resolution. A gold/silicon model system is employed to study interfaces between metals and semiconductors, and multilayers of AlGaAs, Al, and InAs in GaAs are analyzed to explore the ability of C₆₀⁺ to analyze semiconductor interfaces in GaAs. Roughness measurements are reported to differentiate between different factors affecting depth resolution. The best depth resolution from all samples analyzed is achieved using 1 keV Cs⁺. However, C₆₀⁺ sputtering has advantages for analyzing conductor/insulator interfaces because of its high sputter yield, and for analyzing deeper heterolayers in GaAs due to lower sputter-induced roughness.     

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.     

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.     

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.     

Angle of incidence effects in a molecular solid

We investigate the influence of the angle of incidence on the sputter yield when bombarding molecular solid, benzene, with C₆₀. Our simulations show that at normal incidence, essentially all of the projectile energy is deposited into the substrate within ∼2.5 nm of the surface. However, at 75° incident angle, only 35% of the projectile energy is deposited within a depth of less than 1.5 nm of the surface while 65% of the projectile energy is reflected. Therefore, important aspects of the collision process which are dependent upon energy deposition, such as sputter yield, ejection depth, and molecule dissociation, may change as the incident angle changes.     

Characterization and ion-induced degradation of cross-linked poly(methyl methacrylate) studied using time of flight secondary ion mass spectrometry

In this study, a series of random copolymers of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) were prepared as surface-initiated polymer (SIP) films on silicon substrates using atom transfer radical polymerization. Positive and negative ion static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to characterize SIP films with different MMA/EGDMA monomer ratios in an attempt to quantify their surface composition. However, matrix effects in the positive and negative ion modes led to preferential secondary ion generation from the EGDMA monomer and suppression of secondary ions characteristic of the MMA monomer, precluding accurate quantification using standard linear quantification methods. Ion-induced degradation of these films under 5 keV SF₅⁺ bombardment was also examined to determine the effect of cross-linking on the accumulation of ion-induced damage. Increasing incorporation of the EGDMA cross-linker in the SIP films decreased the sputter rate and increased the rate of damage accumulation under extended (>10¹⁴ ions/cm²) 5 keV SF₅⁺ bombardment. Comparison of the ion bombardment data with thermal degradation of cross-linked PMMA suggests that the presence of the cross-linker impedes degradation by depolymerization, resulting in ion-induced damage accumulation. The increased rate of ion-induced damage accumulation with increased cross-link density also suggests that polymers that can form cross-links during ion bombardment are less amenable to depth profiling using polyatomic primary ions.     

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.