MeV Secondary Ion Mass Spectrometry Research Articles

Gold-Assisted Molecular Imaging of Organic Tissue by MeV Secondary Ion Mass Spectrometry.

The quality of molecular imaging by means of MeV primary ion-induced secondary ion mass spectrometry by coating with gold was evaluated on different reference organic molecules and plant samples. The enhancement of the secondary ion yield was evident for the majority of the studied analytes, reaching the highest values at gold thicknesses between 0.5 and 2 nm, and increased the intensity up to 5-fold for reference samples and >2-fold for specific peaks within the plant sample. Improved propagation of the electric field due to the target potential on otherwise electrically insulating plant samples was also evident through improved image resolution and by reducing the background in mass spectra. However, detection of several molecules was significantly decreased at even at 1 nm thick gold layer. The results indicated that an optimized sequence of analysis is required to reliably interpret results.

Chemical Imaging of Organic Materials by MeV SIMS Using a Continuous Collimated Ion Beam

MeV SIMS is a type of secondary ion mass spectrometry (SIMS) technique where molecules are desorbed from the sample surface with ions of MeV energies. In this work, we present a novel system for molecular imaging of organic materials using a continuous analytical beam and a start trigger for timing based on the detection of secondary electrons. The sample is imaged by a collimated primary ion beam and scanning of the target with a lateral resolution of ∼20 μm. The mass of the analyzed molecules is determined with a reflectron-type time-of-flight (TOF) analyzer, where the START signal for the TOF measurement is generated by the secondary electrons emitted from a thin carbon foil (∼5 nm) placed over the beam collimator. With this new configuration of the MeV SIMS setup, a primary ion beam with the highest possible electronic stopping can be used (i.e., highest secondary molecular yield), and samples of any thickness can be analyzed. Since the electrons are collected from the thin foil rather than from the sample surface, the detection efficiency of secondary electrons is always the same for any type of analyzed material. Due to the ability to scan the samples by a piezo stage, samples of a few cm in surface size can be imaged. The imaging capabilities of MeV SIMS are demonstrated on crossing ink lines deposited on paper, a thin section of a mouse brain, and a fingerprint deposited on a thick Si wafer to show the potential application of the presented technique for analytical purposes in biology and forensic science.

MeV TOF SIMS Analysis of Hybrid Organic/Inorganic Compounds in the Low Energy Region.

The low energy range (a few 100 keV to a few megaelectronvolts) primary ion mode in MeV secondary ion mass spectrometry (MeV SIMS) and its potential in exploiting the capabilities of conventional (keV) SIMS and MeV SIMS simultaneously were investigated. The aim is to see if in this energy range of both types of materials, inorganic and organic, can be simultaneously analyzed. A feasibility study was conducted, first by analyzing the dependence of secondary ion yields in indium tin oxide (ITO, In2O5Sn) and leucine (C6H13NO2) on various primary ion energies and charge states of a Cu beam, within the scope of equal influence of electronic and nuclear stopping. Expected behavior was observed for both targets (mainly nuclear sputtering for ITO and electronic sputtering for leucine). MeV SIMS images of samples containing separate regions of Cr and leucine were obtained using both keV and MeV primary ions. On the basis of the image contrast and measured data, the benefit of a low energy beam is demonstrated by Cr+ intensity leveling with leucine [M + H]+ intensity, as opposed to a significant contrast at a higher energy. It is estimated that, by lowering the energy, the leucine [M + H]+ yield efficiency lowers roughly 20 times as a price for gaining about 10 times larger efficiency of Cr+ yield, while the leucine [M + H]+ yield still remains sufficiently pronounced.

W and Tl M-shell X-ray production cross sections induced by carbon ions of energy between 1.56 MeV and 5 MeV

Although PIXE is usually performed with protons, PIXE with heavier ions can be useful in some specific cases. A number of Ion Beam Analysis (IBA) techniques, like ERDA (Elastic Recoil Detection Analysis), NRA (Nuclear Reaction Analysis), AMS (Accelerator Mass Spectrometry), or MeV-SIMS (MeV Secondary Ion Mass Spectrometry), require the use of heavier ions. In such cases the simultaneous use of PIXE could be beneficial. One of the prerequisites for such use of PIXE is good knowledge of X-ray production with heavier ions. In order to update the data base of heavy ion X-ray production cross sections, we have recently started with the systematic study of M-Shell X-ray production induced by carbon ions on heavy elements between W and Bi. Following previous works on Au and Pb (Haidra et al., 2018) and Pt and Bi (Haidra et al., 2019). In this work, we have measured particularly Mαβ, Mγ and total M-shell X-ray production cross section in tungsten and thallium induced by carbon ions of energy range 1.56 MeV to 5 MeV on respective thin targets. The obtained new experimental data are compared to the theoretical predictions given in the framework of the models Plane Wave Born Approximation (PWBA) (Brandt and Lapicki, 1981), ECPSSR (Brandt and Lapicki, 1981) and the Semi-Classical Approximation with united atom (SCA-UA) and separated atom (SCA-SA) correction (Bang and Hansteen, 1957) [5].

Determination of Deposition Order of Toners, Inkjet Inks, and Blue Ballpoint Pen Combining MeV-Secondary Ion Mass Spectrometry and Particle Induced X-ray Emission.

Determination of the deposition order of different writing tools is very important for the forensic investigation of questioned documents. Here we present a novel application of two ion beam analysis (IBA) techniques: secondary ion mass spectrometry using MeV ions (MeV-SIMS) and particle induced X-ray emission (PIXE) to determine the deposition order of intersecting lines made of ballpoint pen ink, inkjet printer ink, and laser printer toners. MeV-SIMS is an emerging mass spectrometry technique where incident heavy MeV ions are used to desorb secondary molecular ions from the uppermost layers of an organic sample. In contrast, PIXE provides information about sample elemental composition through characteristic X-ray spectra coming from greater depth. In the case of PIXE, the information depth depends on incident ion energy, sample matrix and self-absorption of X-rays on the way out from the sample to the X-ray detector. The measurements were carried out using a heavy ion microprobe at the Ruđer Bošković Institute. Principal component analysis (PCA) was employed for image processing of the data. We will demonstrate that MeV-SIMS alone was successful to determine the deposition order of all intersections not involving inkjet printer ink. The fact that PIXE yields information from deeper layers was crucial to resolve cases where inkjet printer ink was included due to its adherence and penetration properties. This is the first time the different information depths of PIXE and MeV-SIMS have been exploited for a practical application. The use of both techniques, MeV-SIMS and PIXE, allowed the correct determination of deposition order for four out of six pairs of samples.

Heavy ion PIXE cross sections in Ti, Zn, Nb, Ru and Ta for 4.8–30.0 MeV oxygen and 3.0–12.0 MeV lithium beams

Heavy ion Particle Induced X-ray Emission (PIXE) spectroscopy offers a number of advantages over standard proton PIXE, such as higher yields and therefore higher sensitivity. However, in order to be able to use heavy ion PIXE more detailed measurements of the ionisation and X-ray cross sections for heavy ions are required. This issue was recognised by one of the Coordinated Research Projects (CRP) of the IAEA on MeV Secondary Ion Mass Spectrometry (SIMS). ANSTO took part in this CRP and we measured X-ray production cross sections on a range of samples for oxygen and lithium beam in the energy range of 4.8–30 MeV and 3–12 MeV, respectively. Here we report on these X-ray production cross section measurements and compare the results with theoretical models. Further energy shifts of the characteristic X-ray lines for the different ion-target combinations are presented and discussed.

Determination of deposition order of blue ballpoint pen lines by MeV Secondary Ion Mass Spectrometry

Secondary Ion Mass Spectrometry using MeV ion excitation was utilised for the analysis of optically indistinguishable intersecting ballpoint pen lines on paper. It was demonstrated that the technique was able to identify different colorants (dyes and synthetic organic pigments) with high efficiency and in a single measurement. The analysis of ink-ink intersections was performed using the Time-of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry. This technique is attached to the heavy ion microprobe at the accelerator facility, and employs focused 8 MeV Si4+ ions for the surface analysis. Molecular imaging allowed for successful identification of sequence deposition order of otherwise optically indistinguishable intersecting lines.

Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples were not embedded in the resin as is usually done when imaging of paint samples using different techniques in the field of cultural heritage.

Time-of-flight MeV-SIMS with beam induced secondary electron trigger

A new Time-of-flight MeV Secondary Ion Mass Spectrometry (MeV-SIMS) setup was developed to be used with a capillary microprobe for molecular imaging with heavy primary ions at MeV energies. Due to the low output current of the ion collimating capillary a Time-of-flight (ToF) measurement method with high duty cycle is necessary. Secondary electrons from the sample surface and transmitted ions were studied as start signals. They enable measurements with a continuous primary beam and unpulsed ToF spectrometer. Tests with various primary ion beams and sample types have shown that a secondary electron signal is obtained from 30% to 40% of incident MeV particles. This provides a ToF start signal with considerably better time resolution than the one obtained from transmitted primary ions detected in a radiation hard gas ionization detector. Beam induced secondary electrons therefore allow for MeV-SIMS measurements with reasonable mass resolution at primary ion beam currents in the low fA range.

Molecular imaging of cannabis leaf tissue with MeV-SIMS method

To broaden our analytical capabilities with molecular imaging in addition to the existing elemental imaging with micro-PIXE, a linear Time-Of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry (MeV-SIMS) was constructed and added to the existing nuclear microprobe at the Jožef Stefan Institute. We measured absolute molecular yields and damage cross-section of reference materials, without significant alteration of the fragile biological samples during the duration of measurements in the mapping mode. We explored the analytical capability of the MeV-SIMS technique for chemical mapping of the plant tissue of medicinal cannabis leaves. A series of hand-cut plant tissue slices were prepared by standard shock-freezing and freeze-drying protocol and deposited on the Si wafer. We show the measured MeV-SIMS spectra showing a series of peaks in the mass area of cannabinoids, as well as their corresponding maps. The indicated molecular distributions at masses of 345.5u and 359.4u may be attributed to the protonated THCA and THCA-C4 acids, and show enhancement in the areas with opened trichome morphology.

Wide area scanning system and carbon microbeams at the external microbeam facility of the INFN LABEC laboratory in Florence

Recently, developments have been made to the external scanning microbeam of INFN-LABEC laboratory in Florence. A new system for mechanical sample scanning was implemented. This system allows us to acquire large maps (up to 20×20cm2), of great interest in the Cultural Heritage field.In parallel, the possibility of using carbon microbeams for experiments, such as, for example, ion beam modification of materials and MeV Secondary Ion Mass Spectrometry, has been investigated.As a test application, Particle Induced X-ray Emission with carbon microbeams has been performed on a lapis lazuli stone.First results for both wide area imaging and external carbon microbeams are briefly reported.

Biomaterial imaging with MeV-energy heavy ion beams

The spatial distribution of several chemical compounds in biological tissues and cells can be obtained with mass spectrometry imaging (MSI). In conventional secondary ion mass spectrometry (SIMS) with keV-energy ion beams, elastic collisions occur between projectiles and atoms of constituent molecules. The collisions produce fragments, making the acquisition of molecular information difficult. In contrast, ion beams with MeV-energy excite near-surface electrons and enhance the ionization of high-mass molecules; hence, SIMS spectra of fragment-suppressed ionized molecules can be obtained with MeV-SIMS. To compare between MeV and conventional SIMS, we used the two methods based on MeV and Bi3-keV ions, respectively, to obtain molecular images of rat cerebellum. Conventional SIMS images of m/z 184 were clearly observed, but with the Bi3 ion, the distribution of the molecule with m/z 772.5 could be observed with much difficulty. This effect was attributed to the low secondary ion yields and we could not get many signal counts with keV-energy beam. On the other hand, intact molecular ion distributions of lipids were clearly observed with MeV-SIMS, although the mass of all lipid molecules was higher than 500Da. The peaks of intact molecular ions in MeV-SIMS spectra allowed us to assign the mass. The high secondary ion sensitivity with MeV-energy heavy ions is very useful in biomaterial analysis.

An electrostatic quadrupole doublet focusing system for MeV heavy ions in MeV-SIMS

The importance of imaging mass spectrometry (MS) for visualizing the spatial distribution of molecular species in biological tissues and cells is growing. In conventional SIMS with keV-energy ion beams, elastic collisions occur between projectiles and atoms in constituent molecules. The collisions produce fragments, making acquisition of molecular information difficult. In contrast, MeV-energy ion beams excite electrons near the surface and enhance the ionization of high-mass molecules, hence, fragment suppressed SIMS spectrum of ionized molecules can be obtained. This work is a further step on our previous report on the successful development of a MeV secondary ion mass spectrometry (MeV-SIMS) for biological samples. We have developed an electrostatic quadrupole doublet (EQ doublet) focusing system, made of two separate lenses, Q1 and Q2, to focus the MeV heavy ion beam and reduce measurement time. A primary beam of 6MeV Cu4+ was focused with this EQ doublet. We applied 1120V to the Q1 lens and 1430V to the Q2 lens, and the current density increased by a factor of about 60. Using this arrangement, we obtained an MeV-SIMS image of 100×100pixels of cholesterol-OH+ of cerebellum (m/z=369.3) over a 4mm×4mm field of view, with a pixel size of 40μm within 5min, showing that our EQ doublet reduces the measurement time of current imaging by a factor of about 30.

Depth profiling of fingerprint and ink signals by SIMS and MeV SIMS

Abstract Police institutions currently have no analytical method of knowing whether a fingerprint was deposited before or after the document was written or printed. The suitability of using MeV secondary ion mass spectrometry (i.e. SIMS with an MeV ion beam) to determine the order in which a fingerprint and written text were deposited on paper was therefore investigated. A 10 MeV O 4+ beam was used to generate secondary ions from the surface of the samples and to map the molecular fragments from doped fingerprints and inks on paper. The images obtained and the sputtering behaviour of the samples was found to be indicative of the sequence of ink and fingerprint deposits.

Matrix‐free high‐resolution imaging mass spectrometry with high‐energy ion projectiles

The importance of imaging mass spectrometry (MS) for visualizing the spatial distribution of molecular species in biological tissues and cells is growing. We have developed a new system for imaging MS using MeV ion beams, termed MeV-secondary ion mass spectrometry (MeV-SIMS) here, and demonstrated more than 1000-fold increase in molecular ion yield from a peptide sample (1154 Da), compared to keV ion irradiation. This significant enhancement of the molecular ion yield is attributed to electronic excitation induced in the near-surface region by the impact of high energy ions. In addition, the secondary ion efficiency for biologically important compounds (>1 kDa) increased to more than 10(10) cm(-2), demonstrating that the current technique could, in principle, achieve micrometer lateral resolution. In addition to MeV-SIMS, peptide compounds were also analyzed with cluster-SIMS and the results indicated that in the former method the molecular ion yields increased substantially compared to the latter. To assess the capability of MeV-SIMS to acquire heavy-ion images, we have prepared a micropatterned peptide surface and successfully obtained mass spectrometric imaging of the deprotonated peptides (m/z 1153) without any matrix enhancement. The results obtained in this study indicate that the MeV-SIMS technique can be a powerful tool for high-resolution imaging in the mass range from 100 to over 1000 Da.