Depth resolution, SIMS

Sputtered Neutral Mass Spectrometry (SNMS) is the mass spectrometric analysis of sputtered atoms ejected from a solid surface by energetic ion bombardment. The sputtered atoms are ionized for mass spectrometric analysis by a mechanism separate from the sputtering atomization. As such, SNMS is complementary to Secondary Ion Mass Spectrometry (SIMS), which is the mass spectrometric analysis of sputtered ions, as distinct from sputtered atoms. The forte of SNMS analysis, compared to SIMS, is the accurate measurement of concentration depth profiles through chemically complex thin-film structures, including interfaces, with excellent depth resolution and to trace concentration levels. Genetically both SALI and GDMS are specific examples of SNMS. In this article we concentrate on post ionization only by electron impact. 

The depth (thickness) of the mixing zone, which limits the depth resolution of a SIMS analysis typically to 2—30 nm, is a function of the energy, angle of incidence,... 

In quadrupole-based SIMS instruments, mass separation is achieved by passing the secondary ions down a path surrounded by four rods excited with various AC and DC voltages. Different sets of AC and DC conditions are used to direct the flight path of the selected secondary ions into the detector. The primary advantage of this kind of spectrometer is the high speed at which they can switch from peak to peak and their ability to perform analysis of dielectric thin films and bulk insulators. The ability of the quadrupole to switch rapidly between mass peaks enables acquisition of depth profiles with more data points per depth, which improves depth resolution. Additionally, most quadrupole-based SIMS instruments are equipped with enhanced vacuum systems, reducing the detrimental contribution of residual atmospheric species to the mass spectrum. 

Roughness from sputtering causes loss of depth resolution in depth profiling for Auger Electron Spectroscopy (AES), X-Ray Photoelectron Spectroscopy (XPS), and SIMS. 

In recent years TOF SIMS has also proved to he a very powerful tool for ultra-shallow depth profiling, having the advantage of simultaneously detecting all elements of interest. The dual beam mode [3.41], in particular, (see Sect. 3.2.2.1) enables optimized depth resolution, because sputtering conditions can be independently optimized. 

Figure 3.17 depicts an ultra-shallow TOF SIMS depth profile of a 100-eV B-implant in Si, capped with 17.3 nm Si. The measurement was performed with 600-eV SF5-sputtering and with 02-flooding. The original wafer surface, into which the B was implanted, is indicated by the maxima of the alkali- and C-signals. Because of these contaminants, a minimum is observed in the °Si-signal. The dynamic range of the B-profile is more than 3.5 decades and the depth resolution is <0.5 nm. 

The limitations of SIMS - some inherent in secondary ion formation, some because of the physics of ion beams, and some because of the nature of sputtering - have been mentioned in Sect. 3.1. Sputtering produces predominantly neutral atoms for most of the elements in the periodic table the typical secondary ion yield is between 10 and 10 . This leads to a serious sensitivity limitation when extremely small volumes must be probed, or when high lateral and depth resolution analyses are needed. Another problem arises because the secondary ion yield can vary by many orders of magnitude as a function of surface contamination and matrix composition this hampers quantification. Quantification can also be hampered by interferences from molecules, molecular fragments, and isotopes of other elements with the same mass as the analyte. Very high mass-resolution can reject such interferences but only at the expense of detection sensitivity. 

Initial results prove the high potential of LA-based hyphenated techniques for depth profiling of coatings and multilayer samples. These techniques can be used as complementary methods to other surface-analysis techniques. Probably the most reasonable application of laser ablation for depth profiling would be the range from a few tens of nanometers to a few tens of microns, a range which is difficult to analyze by other techniques, e. g. SIMS, SNMS,TXRE, GD-OES-MS, etc. The lateral and depth resolution of LA can both be improved by use of femtosecond lasers. 

SIMS has superb surface sensitivity since most of the secondary ions originate within a few nanometers of the surface and since high detection efficiency enables as little as 10 " of a monolayer to be detected for most elements. Because of its very high surface sensitivity, SIMS can be used to obtain depth profiles with exceptionally high depth resolution (<5 nm). Since the beam of primary ions can be focused to a small spot, SIMS can be used to characterize the surface of a sample with lateral resolution that is on the order of micrometers. Elements with low atomic numbers, such as H and He, can be detected, isotope analysis can be conducted, and images showing the distribution of chemical species across... 

State-of-the-art TOF-SIMS instruments feature surface sensitivities well below one ppm of a mono layer, mass resolutions well above 10,000, mass accuracies in the ppm range, and lateral and depth resolutions below 100 nm and 1 nm, respectively. They can be applied to a wide variety of materials, all kinds of sample geometries, and to both conductors and insulators without requiring any sample preparation or pretreatment. TOF-SIMS combines high lateral and depth resolution with the extreme sensitivity and variety of information supplied by mass spectrometry (all elements, isotopes, molecules). This combination makes TOF-SIMS a unique technique for surface and thin film analysis, supplying information which is inaccessible by any other surface analytical technique, for example EDX, AES, or XPS. 

As to expected performance, Figure 8.3 shows some (conservative) values for lateral and in-depth resolutions for various physical methods of analysis. Recent developments already allow better performance, e.g. a lateral resolution of about 0.1 irn with liquid metal ion sources in SIMS and small beams of 150 xm in diameter in [xXPS. 

Sputter-Ion Depth Profiling. Although it is essentially a destructive technique, SIMS depth profiling is rapid, and possesses parts per million or even parts per billion sensitivity to all elements and isotopes, coupled with a depth resolution of a few nanometres. Concentration-depth plots can be accurate to 5%. 

This list incidentally illustrates that the depth resolution of SIMS is of the order of a few atomic layers. 

SIMS and SNMS are versatile analytical techniques for the compositional characterization of solid surfaces and interfaces in materials research.92-94 As one of the most important applications, both surface analytical techniques allow depth profile analysis (concentration profile as a function of the depth analyzed) to be performed in materials science and the semiconductor industry with excellent depth resolution in the low nm range. For depth profiling in materials science, dynamic SIMS and SNMS using high primary ion beam doses are applied. Both techniques permit the analysis of light elements such as H, , C and N, which are difficult to measure with other analytical techniques. 

Depth profiles of matrix elements on Mn- and Co-perovskite layers of fuel cathodes have been measured by LA-ICP-MS in comparison to other well established surface analytical techniques (e.g., SEM-EDX).118 On perovskite layers at a spatial resolution of 100p.m a depth resolution of 100-200 nm was obtained by LA-ICP-MS. The advantages of LA-ICP-MS in comparison to other surface analytical techniques (such as XPS, AES, SIMS, SNMS, GD-OES, GDMS and SEM-EDX) are the speed, flexibility and relatively low detection limits with an easy calibration procedure. In addition, thick oxide layers can be analyzed directly and no charging effects are observed in the analysis of non-conducting thick layers. 

SIMS ions ions ZZ sputtered ions > 1 nm 50 nm + + + > ngg 1 high depth resolution good imaging huge variation of RSCs, intense molecular ions... 

The development of surface analytical techniques such as LA-ICP-MS, GDMS and SIMS focuses on improvements to sensitivity and detection limits in order to obtain precise and accurate analytical data. With respect to surface analytical investigations, an improvement of spatial and depth resolution is required, e.g., by the establishment of a near field effect or the apphcation of fs lasers in LA-ICP-MS. There is a need for the improvement of analytical techniques in the (j,m and nm range, in depth profiling analysis and especially in imaging mass spectrometry techniques to perform surface analyses faster and provide more accurate data on different materials to produce quantitative 3D elemental, isotopic and molecular distribution patterns of increased areas of interest with high spatial and depth resolution over an acceptable analysis time. 

Three direct solid analysis mass spectrometric techniques allowing for lateral and/or depth resolution have been selected in this section laser ablation (LA) coupled to ICP-MS, secondary ion mass spectrometry (SIMS) and GD-MS. 

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