Filters/filtering mass analyzers

SIMS requires an ultra-high vacuum environment, similar to AES and XPS. The ultra-high vacuum environment ensures that trajectories of ions remain undisturbed during SIMS surface analysis. The SIMS vacuum chamber and pumping system is not much different from that for AES and XPS. Figure 8.5 illustrates common SIMS structure in a vacuum chamber in which there are two main components a primary ion system and a mass analyzer system. The primary ion system includes a primary ion source, a Wien filter and ion beam deflector. The mass analysis system includes a secondary ion extractor filter, mass analyzer and ion detector. 

The emitted Ions are collected energy filtered mass analyzed and... 

Rapid scanning mass spectrometers providing unit resolution are routinely used as chroaatographic detectors. Ion separation is accomplished using either a magnetic sector, quadrupole filter or ion trap device. Ions can also be separated by time-of-flight or ion cyclotron resonance mass analyzers but these devices are not widely used with chromatograidiic inlets and will not be discussed here [20]. 

The compatibility is excellent with continuous ion sources such as ESI, dynamic SIMS, CF-FAB, ICP, El, Cl, etc. Sector instalments are not well-suited for pulsed ionization methods, although there are examples where MALDI sources have been utilized [225-229]. Sector instruments are usually larger and more expensive than other mass analyzers, such as TOFs, quadrupole filters, and traps. 

Three-dimensional quadrupole ion trap Quadrupole (RF) ion traps are the newest of the commercially available mass analyzers, despite having been invented at about the same time as the quadrupole mass filter, nearly 50 years ago. The Paul ion trap... 

Fig. 11.16. Representation of three tandem mass spectrometry (MS/MS) scan modes illustrated for a triple quadrupole instrument configuration. The top panel shows the attributes of the popular and prevalent product ion CID experiment. The first mass filter is held at a constant m/z value transmitting only ions of a single mlz value into the collision region. Conversion of a portion of translational energy into internal energy in the collision event results in excitation of the mass-selected ions, followed by unimolecular dissociation. The spectrum of product ions is recorded by scanning the second mass filter (commonly referred to as Q3 ). The center panel illustrates the precursor ion CID experiment. Ions of all mlz values are transmitted sequentially into the collision region as the first analyzer (Ql) is scanned. Only dissociation processes that generate product ions of a specific mlz ratio are transmitted by Q3 to the detector. The lower panel shows the constant neutral loss CID experiment. Both mass analyzers are scanned simultaneously, at the same rate, and at a constant mlz offset. The mlz offset is selected on the basis of known neutral elimination products (e.g., H20, NH3, CH3COOH, etc.) that may be particularly diagnostic of one or more compound classes that may be present in a sample mixture. The utility of the two compound class-specific scans (precursor ion and neutral loss) is illustrated in Fig. 11.17.

The quadrupole mass analyzer is a popular economical choice when known compounds are being analyzed and the filter can be set to a limited number of ions. 

SOZ, NO3, NH4 mass concentration - One-half of each Nuclepore filter was analyzed by Environmental Research and Technology, Inc. (ERT), Westlake Village, California. Their laboratory determined the masses of aerosol sulfate and nitrate on each filter by liquid ion chromatography and ammonium by colorimetry. Based on duplicate analysis of samples and standards the uncertainty in the various determinations per filter were ... 

The aerosol samples collected by the SFU were analyzed both gravimetrlcally for total suspended particulate mass less than 15pm, and by particle induced x-ray emission (PIXE) for elemental content. The filters were weighed before and after sampling using a Cahn 25 electrobalance sensitive to Ipg. Typical precision of TSP determined by this analytical method is 0.5pg/m for samples collected under conditions of low aerosol concentrations ( ). After weighing, the filters were analyzed for elemental content (elements heavier than Na) using the UC Davis PIXE system. This analysis technique is described in Cahill al ( ). 

Mass spectrometric measurements require four components (1) an inlet to introduce the sample (2) a means of ionizing the species of interest (3) mass filtering/separation (4) detection of the ions. Accomplishing this under atmospheric conditions is difficult due to the high sample pressure, which is incompatible with the high voltages used in the ion acceleration region and mass analyzers, and to the complexity of the mixtures found in air. Special considerations imposed by atmospheric conditions are discussed briefly next. 

Two types of mass analyzers have been used extensively in atmospheric applications quadrupole mass filters and time-of-flight (TOF) instruments. The use of ion traps is also being increasingly explored for this application. For the fundamental principles of mass... 

The ions present in the gaseous mixture are sampled through a small hole mounted at the tip of a nose cone situated at the end of the reaction zone and mass analyzed with a quadruple mass filter. 

Figure 3.8 Stability diagram for a linear quadrupole mass analyzer, the first stability region showing a line scan. If the rf and dc voltages applied to the quadrupole are adjusted so that an ion mass m3 is inside the tip of the stability region, then heavier ions of mass m2 and m, and lighter ions m4 are outside the stability region and are filtered out.

In the quadrupole mass analyzer, focusing electrodes direct and accelerate the ionized fragments into a mass filter consisting of four cylindrical electrodes in a vacuum. Tire cylindrical electrodes establish a combination radio-frequency and direct-current electrical field that permits only those ions with a specific, selected mass-to-charge ratio to pass all the way through the filter. The rest of the ions impact die electrodes and do not travel to the exit. Varying the electrical field allows ions with other masses to pass through the filter. 

Figure 10. Experimental scheme for recording NeNePo spectra. The negative ions are mass analyzed in a quadrupole mass filter and introduced into an ion trap. There they are first neutralized (pump), then reionized to a positive ion (probe), so they can escape the trap and enter into another quadrupole mass filter for being detected.

The quadrupole mass filter (QMF) is a mass analyzer on whose operation use of an MEM is not necessarily dependent. The ion currents produced are of sufficient magnitude to be measured by means of a Faraday cage and a suitable amplifier such as a vibrating-reed electrometer. The QMF is a true M/z filter which requires no magnetic fields. Since first being proposed by Paul and Steinwedel (30), the QMF has been investigated extensively, and the principles and methods of operation are well known (see, for example, ref. 31). 

Reactant-ion mass analyzer. Mass analysis is usually achieved in a magnetic sector, although in some apparatuses quadrupole mass filters have been used. 

The complications just described can be minimized if there is greater selectivity in the ionization process, as is sometime possible when photoionization is used as the excitation mechanism. Because the ionization energy can be more precisely controlled, it is possible in selected cases to produce only the desired reactant-ion species, or at least to minimize production of other ions. As already noted in the earlier section on formation of excited ions, it is also possible to populate specific internal-energy states of some reactant ions by using a photoionization source. One of the earliest photoionization mass spectrometers used to study interaction of internally excited ions with neutrals was that constructed by Chupka et al.91 Such apparatuses typically incorporate a photon source (either a line or a continuum source) and an optical monochromator, which are coupled to the reaction chamber. Various types of mass analyzer, including sector type, time-of-flight (TOF), and quadrupole mass filters, have been used with these apparatuses. Chupka has described the basic instrumental configuration in some detail.854 Photoionization mass spectrometers employed to study interactions of excited ions with neutral species have also been constructed in several other laboratories.80,1144,142,143 The apparatus recently developed by LeBreton et al.80 is illustrated schematically in Fig. 7 and is typical of such instrumentation. 

An intermediate resolution mass analyzer is the time of flight mass filter (TOF) [ 18,191- Applied to an ICP it allows resolutions below 1000 m/km. The... 

---