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.

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 Ruder Boskovic 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.

Depth profiling of Cr-ITO dual-layer sample with secondary ion mass spectrometry using MeV ions in the low energy region.

This work explores the possibility of depth profiling of inorganic materials with Megaelectron Volt Secondary Ion Mass Spectrometry using low energy primary ions (LE MeV SIMS), specifically 555 keV Cu2+, while etching the surface with 1 keV Ar+ ions. This is demonstrated on a dual-layer sample consisting of 50 nm Cr layer deposited on 150 nm In2O5Sn (ITO) glass. These materials proved to have sufficient secondary ion yield in previous studies using copper ions with energies of several hundred keV. LE MeV SIMS and keV SIMS depth profiles of Cr-ITO dual-layer are compared and corroborated by atomic force microscopy (AFM) and time-of-flight elastic recoil detection analysis (TOF-ERDA). The results show the potential of LE MeV SIMS depth profiling of inorganic multilayer systems in accelerator facilities equipped with MeV SIMS setup and a fairly simple sputtering source.

Comparison of optical techniques and MeV SIMS in determining deposition order between optically distinguishable and indistinguishable inks from different writing tools.

In the forensic investigation of questioned documents, it is often very important to know the deposition order of ink traces from two different writing tools at their intersection on a paper. In the present work, intersections of inks from several writing tools were studied using optical techniques that are standardly applied for questioned documents examination in a forensic laboratory, and an accelerator-based Ion Beam Analysis (IBA) technique called Secondary Ion Mass Spectrometry using MeV ions (MeV SIMS) that is applied in an accelerator facility. MeV SIMS provides molecular information about the studied inks from writing tools, which is an added value and can be also applied for determination of deposition order but was so far relatively rarely used in forensic studies. Aim of this paper is to compare performance of optical techniques and MeV SIMS for several combinations of intersecting lines. Cases were divided into those in which optical techniques can distinguish used inks and those which are optically completely indistinguishable. In the latter cases, we show that although mass spectra of used inks (from blue ballpoint pens) had extremely small differences, these in combination with advanced and most importantly objective multivariate algorithms could be very beneficial in resolving the deposition order at the intersection of optically indistinguishable inks. In general, MeV SIMS proved to be more efficient for oil-based inks while difficulties were encountered with water-based ones, similar to optical methods.

Emerging nuclear methods for historical painting authentication: AMS-14C dating, MeV-SIMS and O-PTIR imaging, global IBA, differential-PIXE and full-field PIXE mapping.

There is a considerable interest in developing new analytical tools to fight the illicit trafficking of heritage goods and particularly of easel paintings, whose high market values attract an ever-increasing volume of criminal activities. The objective is to combat the illicit traffic of smuggled or forged paintworks and to prevent the acquisition of fakes or looted artefacts in public collections. Authentication can be addressed using various investigation techniques, such as absolute dating, materials characterization, alteration phenomena, etc.; for paintings this remains a challenging task due to the complexity of the materials (paint layers, ground, varnish, canvas, etc.) and preferable use of non-destructive methods. This paper outlines results from concerted action on detecting forged works of art within the framework of a Coordinated Research Project of the International Atomic Energy Agency (IAEA) called Enhancing Nuclear Analytical Techniques to Meet the Needs of Forensic Sciences1. One of the main objectives is to foster the use of emerging Nuclear Analytical Techniques (NAT) using particle accelerators for authentication of paintings, with potential application to other forensics domains, by highlighting their ability to determine painting authenticity and to track restorations or anachronistic clues. The various materials comprising a test painting were investigated using an array of NAT. Binder, canvas and support were directly dated by 14C using Accelerator Mass Spectrometry (14C-AMS); binder and pigments' molecular composition was determined using Secondary Ion Mass Spectrometry with MeV ions (MeV-SIMS); paint layer composition and stratigraphy were accurately determined using Ion Beam Analysis (IBA) and differential Particle-Induced X-ray Emission (PIXE); and pigment spatial distributions were mapped using full-field PIXE. High resolution Optical Photothermal Infrared Spectroscopy (O-PTIR) molecular imaging was also exploited. Obtained results are presented and discussed. It is shown that the combination of the above-mentioned techniques allowed reconstructing the history of the test painting.

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.

Imaging of Organic Samples with Megaelectron Volt Time-of-Flight Secondary Ion Mass Spectrometry Capillary Microprobe.

Time-of-flight Secondary Ion Mass Spectrometry (TOF SIMS) with MeV primary ions offers a fine balance between secondary ion yield for molecules in the mass range from 100 to 1000 Da and beam spot size, both of which are critical for imaging applications of organic samples. Using conically shaped glass capillaries with an exit diameter of a few micrometers, a high energy heavy primary beam can be collimated to less than 10 µm. In this work, imaging capabilities of such a setup are presented for some organic samples (leucine-evaporated mesh, fly wing section, ink deposited on paper). Lateral resolution measurement and molecular distributions of selected mass peaks are shown. The negative influence of the beam halo, an unavoidable characteristic of primary beam collimation with a conical capillary, is also discussed. A new start trigger for TOF measurements based on the detection of secondary electrons released by the primary ion is presented. This method is applicable for a continuous primary ion beam, and for thick targets that are not transparent to the primary ion beam. The solution preserves the good mass resolution of the thin target setup, where the detection of primary ions with a PIN diode is used for a start trigger, reduces the background, and enables a wide range of samples to be analyzed.

Dependence of Megaelectron Volt Time-of-Flight Secondary Ion Mass Spectrometry Secondary Molecular Ion Yield from Phthalocyanine Blue on Primary Ion Stopping Power.

Time-of-flight secondary ion mass spectrometry (TOF SIMS) is a well-established mass spectrometry technique used for the chemical analysis of both organic and inorganic materials. In the last ten years, many advances have been made to improve the yield of secondary molecular ions, especially those desorbed from the surfaces of organic samples. For this reason, cluster ion beams with kiloelectron volt energies for the excitation were mostly used. Alternatively, single-ion beams with megaelectron volt energies can be applied, as was done in the present work. It is well-known that a secondary molecule/ion yield depends strongly on the primary ion stopping power, but the nature of this dependence is not completely clear. Therefore, in the present work, the secondary ion yield from the phthalocyanine blue (C32H16CuN8, organic pigment) was measured for the various combinations of ion masses, energies, and charge states. Measured values were compared with the existing models for ion sputtering. An increase in the secondary yield with the primary ion energy, electronic stopping, velocity, and charge state was found for different types of primary ions. Although this general behavior is valid for all primary ions, there is no single parameter that can describe the measured results for all primary ions at once.