Depth resolution techniques

Depth sensitivity is an equally important consideration in the analysis of surfaces. Techniques based on the detection of electrons or ions derive their surface sensitivity from the fact that these species cannot travel long distances in soflds without undergoing interactions which cause energy loss. If electrons are used as the basis of an analysis, the depth resolution will be relatively shallow and depend on both the energy of the incident and detected electrons and on characteristics of the material. In contrast, techniques based on high energy photons such as x-rays will sample a much greater depth due... 

The physical techniques used in IC analysis all employ some type of primary analytical beam to irradiate a substrate and interact with the substrate s physical or chemical properties, producing a secondary effect that is measured and interpreted. The three most commonly used analytical beams are electron, ion, and photon x-ray beams. Each combination of primary irradiation and secondary effect defines a specific analytical technique. The IC substrate properties that are most frequendy analyzed include size, elemental and compositional identification, topology, morphology, lateral and depth resolution of surface features or implantation profiles, and film thickness and conformance. A summary of commonly used analytical techniques for VLSI technology can be found in Table 3. 

Another confusing issue is that of depth resolution. It is a measurement of the technique s ability to clearly distinguish a property as a function of depth. For example a depth resolution of 20 A, quoted in an elemental composition analysis, means that the composition at one depth can be distinguished from that at another depth if there is at least 20 A between them. 

The SNMS instrumentation that has been most extensively applied and evaluated has been of the electron-gas type, combining ion bombardment by a separate ion beam and by direct plasma-ion bombardment, coupled with postionization by a low-pressure RF plasma. The direct bombardment electron-gas SNMS (or SNMSd) adds a distinctly different capability to the arsenal of thin-film analytical techniques, providing not only matrbe-independent quantitation, but also the excellent depth resolution available from low-energy sputterii. It is from the application of SNMSd that most of the illustrations below are selected. Little is lost in this restriction, since applications of SNMS using the separate bombardment option have been very limited to date. 

Direct sampling of solids may be carried out using laser ablation. In this technique a high-power laser, usually a pulsed Nd-YAG laser, is used to vaporize the solid, which is then swept into the plasma for ionization. Besides not requiring dissolution or other chemistry to be performed on the sample, laser ablation ICPMS (LA-ICPMS) allows spatial resolution of 20-50 pm. Depth resolution is 1-10 pm per pulse. This aspect gives LA-ICPMS unique dit nostic capabilities for geologic samples, surface features, and other inhomogeneous samples. In addition minimal, or no, sample preparation is required. 

Other technique—for example, dynamic secondary ion mass spectrometry or forward recoil spectrometry—that rely on mass differences can use the same type of substitution to provide contrast. However, for hydrocarbon materials these methods attain a depth resolution of approximately 13 nm and 80 nm, respectively. For many problems in complex fluids and in polymers this resolution is too poor to extract critical information. Consequently, neutron reflectivity substantially extends the depth resolution capabilities of these methods and has led, in recent years, to key information not accessible by the other techniques. 

Neutron reflectivity provides a depth resolution of 1 nm and fills an important gap in the resolution between X-ray photoelectron spectroscopy and ion-beam techniques. In this regard, neutron reflectivity promises to play a decisive role in the investigation of solid materials. Equally important is the fact that reflectivity meas-... 

An especially significant application of NRA is the measurement of quantified hydrogen depth profiles, which is difficult using all but a few other analytical techniques. Hydrogen concentrations can be measured to a few tens or hundreds of parts per million (ppm) and with depth resolutions on the order of 10 nm. 

If a sample of polycrystalline material is rotated during the sputtering process, the individual grains will be sputtered from multiple directions and nonuniform removal of material can be prevented. This technique has been successfully used in AES analysis to characterize several materials, including metal films. Figure 9 indicates the improvement in depth resolution obtained in an AES profile of five cycles of nickel and chromium layers on silicon. Each layer is about 50 nm thick, except for a thinner nickel layer at the surface, and the total structure thickness is about 0.5 pm. There can be a problem if the surface is rough and the analysis area is small (less than 0.1-pm diameter), as is typical for AES. In this case the area of interest can rotate on and off of a specific feature and the profile will be jagged. 

Compared with GD-OES (and -MS, if used for depth profiling) SNMS provides somewhat better depth resolution (1 nm range) HE-plasma SNMS hardly suffers from molecule formation in the plasma gas (Ar), as do the CD techniques, in which ar-gides are formed because of the comparatively high pressure. 

The sensitivity and depth resolution of ERDA depend on the type of projectile, on the type of particle, and on energy measurement. Because of the broad range of particles and methods used, general statements about sensitivity and depth resolution are hardly possible. Recent reviews of ERDA techniques are available [3.152-3.154]. 

In principle GD-MS is very well suited for analysis of layers, also, and all concepts developed for SNMS (Sect. 3.3) can be used to calculate the concentration-depth profile from the measured intensity-time profile by use of relative or absolute sensitivity factors [3.199]. So far, however, acceptance of this technique is hesitant compared with GD-OES. The main factors limiting wider acceptance are the greater cost of the instrument and the fact that no commercial ion source has yet been optimized for this purpose. The literature therefore contains only preliminary results from analysis of layers obtained with either modified sources of the commercial instrument [3.200, 3.201] or with homebuilt sources coupled to quadrupole [3.199], sector field [3.202], or time-of-flight instruments [3.203]. To summarize, the future success of GD-MS in this field of application strongly depends on the availability of commercial sources with adequate depth resolution comparable with that of GD-OES. 

The disadvantage of lasers with nanosecond-picosecond pulse duration for depth profiling is the predominantly thermal character of the ablation process [4.229]. For metals the irradiated spot is melted and much of the material is evaporated from the melt. The melting of the sample causes modification and mixing of different layers followed by changes of phase composition during material evaporation (preferential volatilization) and bulk re-solidification [4.230] this reduces the lateral and depth resolution of LA-based techniques. 

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. 

To investigate the interface between polymeric materials, i.e. a so-called buried interfaces, several techniques are available schematically shown in Fig. 4 and listed in Table 2. They have quite different characteristics and depth resolution depending... 

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. 

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