Time-of-flight mass spectrometry of particle emission during irradiation with slow, highly charged ions.

We describe a setup for the analysis of secondary ions and neutrals emitted from solid surfaces and two-dimensional materials during irradiation with highly charged ions. The ultrahigh vacuum setup consists of an electron beam ion source to produce bunches of ions with various charge states q (e.g., Xe1+-Xe46+) and thus potential energies, a deceleration/acceleration section to tune the kinetic energy of the ions in the range of 5 keV to 20 × q keV, a sample stage for laser-cleaning and positioning of freestanding as well as supported samples, a pulsed excimer laser for post-ionization of sputtered neutrals, and a reflectron type time-of-flight mass spectrometer, enabling us to analyze mass and velocity distributions of the emitted particles. With our setup, contributions from potential and kinetic energy deposition can be studied independently of each other. Charge dependent experiments conducted at a constant kinetic energy show a clear threshold for the emission of secondary ions from SrTiO3. Data taken with the same projectile charge state, but at a different kinetic energy, reveal a difference in the ratio of emitted particles from MoS2. In addition, first results are presented, demonstrating how velocity distributions can be measured with the new setup.

A new setup for the investigation of swift heavy ion induced particle emission and surface modifications.

The irradiation with fast ions with kinetic energies of >10 MeV leads to the deposition of a high amount of energy along their trajectory (up to several ten keV/nm). The energy is mainly transferred to the electronic subsystem and induces different secondary processes of excitations, which result in significant material modifications. A new setup to study these ion induced effects on surfaces will be described in this paper. The setup combines a variable irradiation chamber with different techniques of surface characterizations like scanning probe microscopy, time-of-flight secondary ion, and neutral mass spectrometry, as well as low energy electron diffraction under ultra high vacuum conditions, and is mounted at a beamline of the universal linear accelerator (UNILAC) of the GSI facility in Darmstadt, Germany. Here, samples can be irradiated with high-energy ions with a total kinetic energy up to several GeVs under different angles of incidence. Our setup enables the preparation and in situ analysis of different types of sample systems ranging from metals to insulators. Time-of-flight secondary ion mass spectrometry enables us to study the chemical composition of the surface, while scanning probe microscopy allows a detailed view into the local electrical and morphological conditions of the sample surface down to atomic scales. With the new setup, particle emission during irradiation as well as persistent modifications of the surface after irradiation can thus be studied. We present first data obtained with the new setup, including a novel measuring protocol for time-of-flight mass spectrometry with the GSI UNILAC accelerator.

Investigating the Fundamentals of Molecular Depth Profiling Using Strong-field Photoionization of Sputtered Neutrals.

Molecular depth profiles of model organic thin films were performed using a 40 keV C60+ cluster ion source in concert with TOF-SIMS. Strong-field photoionization of intact neutral molecules sputtered by 40 keV C60+ primary ions was used to analyze changes in the chemical environment of the guanine thin films as a function of ion fluence. Direct comparison of the secondary ion and neutral components of the molecular depth profiles yields valuable information about chemical damage accumulation as well as changes in the molecular ionization probability. An analytical protocol based on the erosion dynamics model is developed and evaluated using guanine and trehalose molecular secondary ion signals with and without comparable laser photoionization data.

Ionization effects in molecular depth profiling of trehalose films using buckminsterfullerene (C60) cluster ions.

Salts play a mysterious role in desorption mass spectrometry, especially in biological samples.[1] We used trehalose films doped with a peptide as a well defined model system to investigate the ionization effects in organic molecular depth profiling. Sodium salts at 1% level were added into the solution used to produce the trehalose films, and depth profiles were obtained with a C60 ion source. The results show that the protonated molecular ion signal from the peptide and the quasimolecular ion signal of trehalose are significantly suppressed by the addition of salts, whereas the signals representing salt clusters and salt adducts of trehalose are formed in both positive and negative modes. The formation of protonated molecular ions is found to correlate with the ratio between protonated and bare water ions, suggesting that the latter can be used as an indicator for the accumulation of protons liberated by the ion bombardment. In experiments where no salt was added, it is shown that the surface variation of the protonated molecular ion signal strongly depends upon the water content of the trehalose film.

Fundamental studies of molecular depth profiling using organic delta layers as model systems.

Alternating Langmuir-Blodgett multilayers of barium arachidate (AA) and barium dimyristoyl phosphatidate (DMPA) were used to elucidate the factors that control depth resolution in molecular depth profiling experiments. More specifically, thin (4.4 nm) layers of DMPA were embedded in relatively thick (~50 nm) multilayer stacks of AA, resulting in a well-defined delta-layer model system closely resembling a biological membrane. This system was subjected to a three-dimensional imaging depth profile analysis using a focused buckminsterfullerene (C60) cluster ion beam. The depth response function measured in these experiments exhibits similar features as those determined in inorganic depth profiling: namely, an asymmetric shape with quasi-exponential leading and trailing edges and a central Gaussian peak. The magnitude of the corresponding characteristic rise and decay lengths is found to be 5 and 16 nm, respectively, while the total half width of the response function characterizing the apparent depth resolution was about 29 nm. Ion-induced mixing is proposed to be largely responsible for the broadening, rather than topography, as determined by atomic force microscopy.

Strong-field Photoionization of Sputtered Neutral Molecules for Molecular Depth Profiling.

Molecular depth profiles of an organic thin film of guanine vapor deposited onto a Ag substrate are obtained using a 40 keV C(60) cluster ion beam in conjunction with time-of-flight secondary ion mass spectrometric (ToF-SIMS) detection. Strong-field, femtosecond photoionization of intact guanine molecules is used to probe the neutral component of the profile for direct comparison with the secondary ion component. The ability to simultaneously acquire secondary ions and photoionized neutral molecules reveals new fundamental information about the factors that influence the properties of the depth profile. Results show that there is an increased ionization probability for protonated molecular ions within the first 10 nm due to the generation of free protons within the sample. Moreover, there is a 50% increase in fragment ion signal relative to steady state values 25 nm before reaching the guanine/Ag interface as a result of interfacial chemical damage accumulation. An altered layer thickness of 20 nm is observed as a consequence of ion beam induced chemical mixing. In general, we show that the neutral component of a molecular depth profile using the strong-field photoionization technique can be used to elucidate the effects of variations in ionization probability on the yield of molecular ions as well as to aid in obtaining accurate information about depth dependent chemical composition that cannot be extracted from TOF-SIMS data alone.

Three-dimensional depth profiling of molecular structures.

Molecular time of flight secondary ion mass spectrometry (ToF-SIMS) imaging and cluster ion beam erosion are combined to perform a three-dimensional chemical analysis of molecular films. The resulting dataset allows a number of artifacts inherent in sputter depth profiling to be assessed. These artifacts arise from lateral inhomogeneities of either the erosion rate or the sample itself. Using a test structure based on a trehalose film deposited on Si, we demonstrate that the "local" depth resolution may approach values which are close to the physical limit introduced by the information depth of the (static) ToF-SIMS method itself.

Kinetic electron excitation in atomic collision cascades.

The kinetic excitation of electrons upon bombardment of a solid surface with energetic ions is investigated. Using a metal-insulator-metal junction, hot electrons produced by the projectile impact are detected with excitation energies well below the vacuum level. The results provide information that cannot be accessed by electron emission experiments. The observed tunneling current depends on the projectile energy and the bias voltage across the junction, opening the possibility of internal excitation spectroscopy.

Vacuum ultraviolet single photon versus femtosecond multiphoton ionization of sputtered germanium clusters.

Neutral atoms and clusters desorbed from a solid germanium surface by ion bombardment are detected by laser postionization and time-of-flight mass spectrometry. Two different photoionization schemes are compared which are generally believed to be candidates for the 'soft' ionization of polyatomic species without significant photon induced fragmentation. First, a single photon ionization process is employed using an F2 laser as an intense VUV source with a photon energy in excess of all relevant ionization potentials. It is shown that the available laser pulse energy is sufficient to saturate the ionization of Ge atoms and all detected Ge(n) clusters. The resulting mass spectra are compared to those obtained with a non-resonant multiphoton ionization process using a high intensity laser delivering pulses of 250 femtoseconds duration at a wavelength of 267 nm. Also in this case, the ionization process can apparently be driven into saturation. The mass spectra measured under these conditions are found to be almost identical to those obtained using single photon ionization. We take this as an indication that the results obtained with both postionization techniques closely reflect the true cluster sputtering yields and, in particular, are not dominated by photon induced fragmentation.

Relative elemental sensitivity factors in non-resonant laser-SNMS.

Using a reflectron time-of-flight mass spectrometer, the ionization process in non-resonant Laser postionization Secondary Neutral Mass Spectrometry (SNMS) has been investigated. In particular, the postionization efficiencies (PIE) achieved by multi photon and single photon absorption have been compared by ionizing ten elements sputtered from a NIST standard reference material by excimer laser radiation of 248 nm, 193 nm and 157 nm. Only in the case of single photon ionization (SPI) the measured laser intensity dependence of the PIE can be understood quantitatively in terms of corresponding theory. From the results, absolute values of the SPI cross sections have been evaluated for atoms of nine elements, which show a total variation over about two orders of magnitude. Furthermore, even in the regime of high laser intensity, where the ionization of all atoms is completely saturated, different elements have been detected with relative sensitivity factors which scatter over about one order of magnitude. This has been attributed to element dependent variations of the effective ionization volume which are caused by the different kinetic energy and angular distributions of different sputtered atoms.