Molecular depth profiling of multilayer structures of organic semiconductor materials by secondary ion mass spectrometry with large argon cluster ion beams

In this study, we present molecular depth profiling of multilayer structures composed of organic semiconductor materials such as tris(8‐hydroxyquinoline)aluminum (Alq₃) and 4,4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl (NPD). Molecular ions produced from Alq₃ and NPD were measured by linear‐type time‐of‐flight (TOF) mass spectrometry under 5.5 keV Ar₇₀₀ ion bombardment. The organic multilayer films were analyzed and etched with large Ar cluster ion beams, and the interfaces between the organic layers were clearly distinguished. The effect of temperature on the diffusion of these materials was also investigated by the depth profiling analysis with Ar cluster ion beams. The thermal diffusion behavior was found to depend on the specific materials, and the diffusion of Alq₃ molecules was observed to start at a lower temperature than that of NPD molecules. These results prove the great potential of large gas cluster ion beams for molecular depth profiling of organic multilayer samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular depth profiling with cluster ion beams

Peptide-doped trehalose thin films have been characterized by bombardment with energetic cluster ion beams of C60+ and Aux+ (x = 1, 2, 3). The aim of these studies is to acquire information about the molecular sputtering process of the peptide and trehalose by measurement of secondary ion mass spectra during erosion. This system is important since uniform thin films of approximately 300 nm thickness can be reproducibly prepared on a Si substrate, allowing detailed characterization of the resulting depth profile with different projectiles. The basic form of the molecular ion intensity as a function of ion dose is described by a simple analytical model. The model includes parameters such as the molecular sputtering yield, the damage cross section of the trehalose or the peptide, and the thickness of a surface layer altered by the projectile. The results show that favorable conditions for successful molecular depth profiling are achieved when the total sputtering yield is high and the altered layer thickness is low. Successful molecular depth profiles are achieved with all of the cluster projectiles, although the degree of chemical damage accumulation was slightly lower with C60. With C60 bombardment, the altered layer thickness of about 20 nm and the damage cross section of about 5 nm2 are physically consistent with predictions of molecular dynamics calculations available for similar chemical systems. In general, the model presented should provide guidance in optimizing experimental parameters for maximizing the information content of molecular depth profiling experiments with complex molecular thin film substrates.     

Carbon-13 labeling for improved tracer depth profiling of organic materials using secondary ion mass spectrometry

13C labeling is introduced as an alternative to deuterium labeling for analysis of organic materials using secondary ion mass spectrometry (SIMS). A model macromolecular system composed of polystyrene (PS) and poly(methyl methacrylate) (PMMA) was used to compare the effects of isotopic labeling using both deuterium substitution (dPS) and 13C labeling (13C-PS). Clear evidence is shown that deuterium labeling does introduce changes in the thermodynamic properties of the system, with the observation of segregation of dPS to an hPS:dPS/hPMMA interface. This type of behavior could significantly impact many types of investigations due to the potential for improper interpretation of experimental results as a consequence of labeling-induced artifacts. 13C labeling is shown to provide a true tracer for analysis using SIMS.     

Surface analysis of polymer materials by secondary ion mass spectrometry

Atomic as well as molecular secondary ions are emitted from the uppermost monolayer of a solid during ion bombardment. Mass analysis of these positive and negative secondary ions supplies detailed information on the chemical composition of the bombarded surface. High mass range (> 10,000 u), high mass resolution (m/Δm > 10,000), accurate mass determination (ppm range) and high sensitivity (ppm of a monolayer) are achieved by applying time-of-flight (TOF) mass analyzers. TOF-SIMS has been successfully applied to a wide variety of polymer materials, including polymer blends, chemically or plasma modified surfaces, and plasma polymerization layers. Detailed information on the composition of repeat units, endgroups, oligomer distributions, additives, as well as surface contaminants can be obtained. Basic concepts of TOF-SIMS will be described and typical analytical examples for the characterization of polymer materials will be presented.     

Atomic/molecular depth profiling of nanometric‐metallized polymer thin films by secondary ion mass spectrometry

The capability of secondary ion mass spectrometry (SIMS) to perform atomic and molecular in‐depth analysis in complex nanometric‐metallized thin polymer films used to manufacture capacitors is demonstrated through three different case studies related to failure analysis. The excellent repeatability and sensitivity of the technique allow us to study the degradation process of the nanometric‐metallized layer in the capacitor films and the accurate location of the metal‐polymer interface. The analysis of the sample is challenging due to the extreme difference in conductivity between layers, and the reduced thickness of the metallization grown on top of a rough polymeric base. However, SIMS has provided reliable and reproducible results with relative standard deviation (RSD) values better than 1.5% in the metallic layer thickness estimation. The detailed information of atomic and molecular ion in‐depth distributions provided by SIMS depth profiling has allowed the identification of different factors (demetallization, generation of interstitial oxide regions, and diffusion processes or modification in the metallization thickness) that can be directly related to the origin of the lack of performance of the mounted devices. Copyright © 2010 John Wiley & Sons, Ltd.     

Lipid imaging with cluster time-of-flight secondary ion mass spectrometry

This brief article provides an overview of the current state of the art in biological imaging mass spectrometry using cluster time-of-flight secondary ion mass spectrometry (TOF–SIMS). Recent and spectacular improvements in terms of sensitivity of TOF–SIMS imaging methods have allowed many biological applications to recently be successfully tested, such as mapping of lipid disorders in human muscles of a patient suffering from dystrophy, localization of surfactins after the swarming of bacteria on a surface, or lipid mapping over whole-body animal sections.     

Energy‐resolved depth profiling of metal‐polymer interfaces using dynamic quadrupole secondary ion mass spectrometry

Quadrupole secondary ion mass spectrometry (qSIMS) characterization of a metallized polypropylene film used in the manufacturing of capacitors has been performed. Ar⁺ primary ions were used to preserve the oxidation state of the surface. The sample exhibits an incomplete metallization that made it difficult to determine the exact location of the metal‐polymer interface due to the simultaneous contribution of ions with identical m/z values from the metallic and the polymer layers. Energy filtering by means of a 45° electrostatic analyzer allowed resolution of the metal‐polymer interface by selecting a suitable kinetic energy corresponding to the ions generated in the metallized layer but not from the polymer. Under these conditions, selective analyses of isobaric interferences such as ²⁷Al⁺ and ²⁷C₂H or ⁴³AlO⁺ and ⁴³C₃H have been successfully performed. Copyright © 2009 John Wiley & Sons, Ltd.     

Quantitative depth profiling of argon in tungsten films by secondary ion mass spectrometry.

Depth profiling of Ar in Ar-implanted tungsten (W) films with an excellent detection limit was investigated by secondary ion mass spectrometry (SIMS). Depth profiles of Ar with the detection of Ar+ and ArCs+ secondary ions, which were produced by O2+ and Cs+ primary ions, respectively, were compared in view of the detection limit and the depth resolution. The detection limit of Ar monitoring Ar+ was limited by the carbon- and oxygen-containing molecular ion (C2O+) in the sample as well as in the SIMS instrument. It was observed that some of the Ar+ ions were produced in the vacuum above the sample surfaces, whereas the ionization of almost all C2O+ occurred at the samples. By using different energy spectra between Ar+ and C2O+, we showed that the energy-filtering technique is advantageous for suppressing C2O+ ion detection. It is also confirmed that the ArCs+ secondary ion is only slighting by the C2OCs+ mass-interference ion. A detection limit of 4 x 10(18) cm(-3) for monitoring Ar+ and 3 x 10(16) cm(-3) for monitoring ArCs+ was achieved under a primary-ion current density of 0.16 mA/cm2. The detection of ArCs+ ion rather than Ar+ was found to be superior in the detection limit and the depth resolution. We conclude that SIMS is useful for the determination of the Ar depth distribution in W films.     

Quantitative secondary ion mass spectrometry depth profiling of surface layers of cubic silver halide microcrystals

The present article describes depth-profiling studies on populations of cubic silver halide microcrystals (typical size between 400 and 600 nm). These crystals consist of mixed halides (Cl, Br, I) and are characterized by internal halide distributions such as core-shell structures. Determination of the spatial distribution of the different halides in the microcrystals offers valuable information for the optimization of the crystal design of new photographic materials. The first part describes the calibration of the sputtered depth, which is more complicated than in the one-dimensional case of flat surfaces. In a second part, three different quantification methods [halide intensity ratios, XCs₂⁺ detection (X=halide) and the infinite velocity method] are used to determine the mean composition of the surface layer as a function of sputtered depth in the silver halide crystals. Although particles of submicrometer size are obviously not the ideal samples for depth profiling, a good correlation with values obtained by scanning electron microscopy energy dispersive X-ray microanalysis and wavelength dispersive X-ray fluorescence bulk analysis could be achieved.     

Method for improved secondary ion yields in cluster secondary ion mass spectrometry

A method to increase useful yields of organic molecules is investigated by cluster secondary ion mass spectrometry (SIMS). Glycerol drops were deposited onto various inkjet‐printed arrays and the organic molecules in the film were rapidly incorporated into the drop. The resulting glycerol/analyte drops were then probed with fullerene primary ions under dynamic SIMS conditions. High primary ion beam currents were shown to aid in the mixing of the glycerol drop, thus replenishing the probed area and sustaining high secondary ion yields. Integrated secondary ion signals for tetrabutylammonium iodide and cocaine in the glycerol drops were enhanced by more than a factor of 100 compared with an analogous area on the surface, and a factor of 1000 over the lifetime of the glycerol drop. Once the analyte of interest is incorporated into the glycerol microdrop, the solution chemistry can be tailored for enhanced secondary ion yields, with examples shown for cyclotrimethylenetrinitramine (RDX) chloride adduct formation. In addition, depositing localized glycerol drops may enhance analyte secondary ion count rates to high enough levels to allow for site‐specific chemical maps of molecules in complex matrices such as biological tissues. Published in 2010 by John Wiley & Sons, Ltd.     

Biological tissue imaging with time-of-flight secondary ion mass spectrometry and cluster ion sources

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) using liquid metal ion guns (LMIGs) is now sensitive enough to produce molecular-ion images directly from biological tissue samples. Primary cluster ions strike a spot on the sample to produce a mass spectrum. An image of this sample is achieved by rastering the irradiated point over the sample surface. The use of secondary ion mass spectrometry for mapping biological tissue surfaces provides unique analytical capabilities; in particular, it enables in a single acquisition a large variety of biological compounds to be localised on a micrometer scale and scrutinised for colocalisations. Without any treatment of the sample, this method is fully compatible with subsequent and complementary analyses like fluorescence microscopy, histochemical staining, or even matrix-assisted laser desorption/ionisation imaging. Basic physical concepts, required instrumentation (ion source and mass analyzer), sample preparation methods, image acquisition, image processing, and emerging biological applications will be described and discussed.     

Sensitivity enhancement using chemically reactive gas cluster ion beams in secondary ion mass spectrometry (SIMS)

We report for the first time on significant molecular secondary ion yield increases by modifying the chemistry of a water cluster primary ion beam. This was demonstrated using 70-keV ion beams of 0.15 eV/amu. For the neutral drug Bezafibrate, secondary ion yield enhancements ×5–10 were observed when replacing the Ar carrier gas in a water gas cluster ion beam (GCIB) source with a mixture containing 12% CO₂ and 2% O₂ in Ar. For the cationic drug Ranitidine, the ion yield enhancements using the CO₂-containing carrier gas were up to ×20–50 in positive mode and ×2–4 in negative mode. The extent of molecular fragmentation was very similar from both cluster beams. We conclude that additional chemically reactive species are present in the impact zone using the (H₂O/CO₂)_n projectile, which promote the formation of secondary ions of both polarity through projectile impact-induced chemical reactions. This methodology can be applied to further extend the capabilities of high-resolution 3-dimensional mass spectral imaging using reactive GCIB-SIMS.     

Electrospray droplet impact/secondary ion mass spectrometry: cluster ion formation

The electrospray droplets that are sampled through an orifice into the vacuum chamber are accelerated by 10 kV and impact on the stainless steel substrate. The mass and the kinetic energy of electrospray droplets are roughly estimated to be a few 10(6) u and approximately 10(6) eV, respectively. The molecular ion M(+.) and the protonated molecule [M+H](+) are observed as secondary ions for chrysene and coronene deposited on the metal substrate (no matrix used). The ionization may take place in the shock wave generated by the high-momentum coherent collision between the droplet projectile and the solid sample. Cluster ions of H(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n), with n up to approximately 150, were observed as secondary ions formed by the electrospray droplet impact ionization (EDI) for 10(-2) M trifluoroacetic acid (TFA) aqueous solution. This indicates that the charged droplets that collide with the metal substrate with the kinetic energy of approximately 10(6) eV do not vaporize completely but are disintegrated into many tiny microdroplets. The ion signal intensity anomalies (i.e. magic numbers) were observed for the cluster ions of H(3)O(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n) for 10(-2) M TFA aqueous solution and of Cs(+)(H(2)O)(n), I(-)(H(2)O)(n), Cs(+)(CsI)(n), and I(-)(CsI)(n) for 10(-2) M CsI aqueous solution.     

Ultra-low-angle microtomy and static secondary ion mass spectrometry for molecular depth profiling of UV-curable acrylate multilayers at the nanoscale

Development of sustainable materials requires methods capable of probing the molecular composition of samples not only at the surface but also in depth. Static secondary ion mass spectrometry (S-SIMS) characterises the distribution of organic and inorganic compounds at the surface. Ultra-low-angle microtomy (ULAM) has been studied as an alternative or complementing method to the molecular depth profiling with, e.g. C₆₀⁺ projectiles. Acrylate-based multilayers relevant to industrial inkjet printing have been sectioned at a cutting angle below 1°. In this way, analysis of the section over a distance of 1 μm allows a depth range in the order of a few nm in the original sample to be achieved. Adequate procedures to optimise the ULAM step and minimise or control the cutting artefacts have been developed. The combination of ULAM with S-SIMS has allowed a depth resolution of 10 nm to be obtained for components at a distance of 35 μm from the surface.     

Characterization of high explosive particles using cluster secondary ion mass spectrometry

The use of secondary ion mass spectrometry (SIMS) for the detection and spatially resolved analysis of individual high explosive particles is described. A C(8) (-) carbon cluster primary ion beam was used in a commercial SIMS instrument to analyze samples of high explosives dispersed as particles on silicon substrates. In comparison with monatomic primary ion bombardment, the carbon cluster primary ion beam was found to greatly enhance characteristic secondary ion signals from the explosive compounds while causing minimal beam-induced degradation. The resistance of these compounds to degradation under ion bombardment allows explosive particles to be analyzed under high primary ion dose bombardment (dynamic SIMS) conditions, facilitating the rapid acquisition of spatially resolved molecular information. The use of cluster SIMS combined with computer control of the sample stage position allows for the automated identification and counting of explosive particle distributions on silicon surfaces. This will be useful for characterizing the efficiency of transfer of particulates in trace explosive detection portal collectors and/or swipes utilized for ion mobility spectrometry applications.     

Multilayer thin-film coatings based on chromium nitride and aluminum nitride: Comparative depth profiling by secondary ion mass spectrometry and glow-discharge optical emission spectrometry

Round-robin characterization is reported on the sputter depth profiling of CrN/AlN multilayer thin-film coatings on nickel alloy by secondary ion mass spectrometry (SIMS) and glow-discharge optical emission spectrometry (GD-OES). It is demonstrated that a CAMECA SIMS 4550 Depth Profiler operated with 3 keV O ₂ ⁺ primary ions provides the best depth resolution and sensitivity. The key factor is sample rotation, which suppresses the negative influence of the surface topography (initial and ion-induced) on the depth profile characteristics.