In this work, we explored the possibility of performing molecular depth-profiling by using very low-energy (about 200 eV) monoatomic Cs(+) ions. We show, for the first time, that this simple approach is successful on polymer layers of polycarbonate (PC). Under 200 eV Cs(+) irradiation of PC, a fast decrease of all characteristic negatively charged molecular ion signals is first observed but, rather surprisingly, these signals reach a minimum before rising again. A steady state is reached at which time most specific PC fragments are detected, some with even higher signal intensity (e.g. C(6)H(5)O(-)) than before irradiation. It is believed that the implanted Cs plays a major role in enhancing the negative ionisation of molecular fragments, leading to their easy detection for all the profile, although some material degradation obviously occurs. In the positive ion mode, all molecular fragments of the polymer disappear very rapidly, but clusters combining two Cs atoms and one molecular fragment (e.g. Cs(2)C(6)H(5)O(+)) are detected during the profile, proving that some molecular identification remains possible. In conclusion, this work presents a simple approach to molecular depth-profiling, complementary to cluster ion beam sputtering.

The advantages and drawbacks of using either monatomic or buckminsterfullerene primary ions for metal-assisted secondary ion mass spectrometry (MetA-SIMS) are investigated using a series of organic samples including additive molecules, polyolefins, and small peptides. Gold deposition is mostly performed by sputter-coating, and in some cases, the results are compared to those of thermal evaporation (already used in a previous article: Delcorte, A.; Médard, N.; Bertrand, P. Anal. Chem. 2002, 74, 4955). The microstructure of the gold-covered sample surfaces is assessed by scanning and transmission electron microscopies. The merits of the different sets of experimental conditions are established via the analysis of fragment and parent-like ion yields. For most of the analyzed samples, the highest yields of fragment and parent-like ions are already reached with the sole use of C60+ projectiles. Metallization of the sample does not lead to a significant additional enhancement. For polyethylene and polypropylene, however, gold metallization associated with Ga+/In+ projectiles appears to be the only way to observe large cationized, sample-specific chain segments (m/z approximately 1000-2000). A detailed study of the polypropylene mass spectra as a function of gold coverage shows that the dynamics of yield enhancement by metal nanoparticles is strongly dependent on the choice of the projectile, e.g., a pronounced increase with Ga+ and a slow decay with C60+. The cases of Irganox 1010, a polymer antioxidant, and leucine enkephalin, a small peptide, allow us to investigate the specific influence of the experimental conditions on the emission of parent(like) ions such as M+, (M + Na)+, and (M + Au)+. The results show a dependence on both the type of sample and the considered secondary ion. Using theoretical and experimental arguments, the discussion identifies some of the mechanisms underlying the general trends observed in the results. Guidelines concerning the choice of the experimental conditions for MetA-SIMS are provided.

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Novel cyanoterphenyl self-assembly monolayers on Au(111) studied by ellipsometry, x-ray photoelectron spectroscopy, and vibrational spectroscopies Interaction of self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiols with water studied by vibrational sum-frequency generation Surface elemental and structural characterization of hexadecanethiol and heptadecanethiol (C 16 and C 17 for short͒ and 16,16,16-trifluorohexadecanethiol (FC 16 ) self-assembled monolayers ͑SAMs͒ on a Au͕111͖ surface have been obtained from time-of-flight scattering and recoiling spectrometry. The clean Au surface was also characterized in order to identify the azimuthal orientation of the SAMs with respect to the substrate. Classical ion trajectory simulations were used to relate the experimental scattering and recoiling data to the surface structure. The scattered and recoiled atoms originate from the outermost five-six atomic layers, and azimuthal anisotropy was observed in the measurements. The results provide a model for the SAMs in which the alkyl chains chemisorb with the S atoms situated above the face-centered-cubic ͑fcc͒ threefold sites of the Au͕111͖ surface to form a continuous film with a (ͱ3ϫͱ3)R30°structure that fully covers the Au surface. The orientation of the molecular axis azimuth of the SAMs relative to the Au azimuthal directions was determined. The data indicate that the molecular chains have specific tilt and twist angles relative to the Au surface and six coexisting domains resulting from the six equivalent tilt directions of the molecular axis. Dramatic changes in the anisotropic patterns of the ion scattering azimuthal scans from the surfaces of the SAMs with different terminations were observed. These phenomena result from the different tilt angles of the CH 3 and CF 3 groups. The data are consistent with free rotation of both the CH 3 and CF 3 groups. The C 16 SAM exhibited the best azimuthal features and was more resistant to radiation damage from the incident Ar ϩ scattering beam than the other films. Due to the tilt angle of the SAMs, an ''ion's eye view'' of the structure, i.e., the positions of the atomic cores as experienced by the incoming keV ions, reveals a regular array of sloping cavities within each unit cell.

With the recent developments in secondary ion mass spectrometry (SIMS), it is now possible to obtain molecular depth profiles and 3D molecular images of organic thin films, i.e. SIMS depth profiles where the molecular information of the mass spectrum is retained through the sputtering of the sample. Several approaches have been proposed for "damageless" profiling, including the sputtering with SF5(+) and C60(+) clusters, low energy Cs(+) ions and, more recently, large noble gas clusters (Ar500-5000(+)). In this article, we evaluate the merits of these different approaches for the in depth analysis of organic photovoltaic heterojunctions involving poly(3-hexylthiophene) (P3HT) as the electron donor and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as the acceptor. It is demonstrated that the use of 30 keV C60(3+) and 500 eV Cs(+) (500 eV per atom) leads to strong artifacts for layers in which the fullerene derivative PCBM is involved, related to crosslinking and topography development. In comparison, the profiles obtained using 10 keV Ar1700(+) (∼6 eV per atom) do not indicate any sign of artifacts and reveal fine compositional details in the blends. However, increasing the energy of the Ar cluster beam beyond that value leads to irreversible damage and failure of the molecular depth profiling. The profile qualities, apparent interface widths and sputtering yields are analyzed in detail. On the grounds of these experiments and recent molecular dynamics simulations, the discussion addresses the issues of damage and crater formation induced by the sputtering and the analysis ions in such radiation-sensitive materials, and their effects on the profile quality and the depth resolution. Solutions are proposed to optimize the depth resolution using either large Ar clusters or low energy cesium projectiles for sputtering and/or analysis.

Ion beam depth profiling is increasingly used to investigate layers and interfaces in complex multilayered devices, including solar cells. This approach is particularly challenging on hybrid perovskite layers and perovskite solar cells because of the presence of organic/inorganic interfaces requiring the fine optimization of the sputtering beam conditions. The ion beam sputtering must ensure a viable sputtering rate on hard inorganic materials while limiting the chemical (fragmentation), compositional (preferential sputtering) or topographical (roughening and intermixing) modifications on soft organic layers. In this work, model (Csx(MA0.17FA0.83)100−xPb(I0.83Br0.17)3/cTiO2/Glass) samples and full mesoscopic perovskite solar cells are profiled using low-energy (500 and 1000 eV) monatomic beams (Ar+ and Cs+) and variable-size argon clusters (Arn+, 75 < n < 4000) with energy up to 20 keV. The ion beam conditions are optimized by systematically comparing the sputtering rates and the surface modifications associated with each sputtering beam. X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and in-situ scanning probe microscopy are combined to characterize the interfaces and evidence sputtering-related artifacts. Within monatomic beams, 500 eV Cs+ results in the most intense and stable ToF-SIMS molecular profiles, almost material-independent sputtering rates and sharp interfaces. Large argon clusters (n > 500) with insufficient energy (E < 10 keV) result in the preferential sputtering of organic molecules and are highly ineffective to sputter small metal clusters (Pb and Au), which tend to artificially accumulate during the depth profile. This is not the case for the optimized cluster ions having a few hundred argon atoms (300 < n < 500) and an energy-per-atom value of at least 20 eV. In these conditions, we obtain (i) the low fragmentation of organic molecules, (ii) convenient erosion rates on soft and hard layers (but still different), and (iii) constant molecular profiles in the perovskite layer, i.e., no accumulation of damages.

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