Sputtering rate, SIMS

If it is required that the surface of the sample remains undisturbed during analysis, SIMS must be carried out at very low surface removal rates, typically about 10 monolayer/s. The terms static and dynamic are used to divide the sputtering rate of the sample into regimes where only surface species are observed (static SIMS) or where surface and bulk species are observed (dynamic SIMS). The static limit is usually considered to be <10 ions/cm impinging on the sample surface. Under these conditions, only about 1/1000 atoms on the surface of the sample are struck by a primary ion. 

GDS instruments are viable alternatives to the traditional arc and spark-source spectroscopies for bulk metals analysis. Advantages of GDS over surface analysis methods such as AES, XPS and SIMS are that an ultrahigh vacuum is not needed and the sputtering rate is relatively high. In surface analysis, GD-OES, AES, XPS and SIMS will remain complementary techniques. GD-OES analysis is faster than AES (typically 10 s vs. 15 min). GD-OES is also 100 times more sensitive than... 

The time necessary for removing one monolayer during a SIMS experiment depends not only on the sputter yield, but also on the type of sample under study. We will make an estimate for two extremes. First, the surface of a metal contains about 1015 atoms/cm2. If we use an ion beam with a current density of 1 nA/cm2, then we need some 150 000 s - about 40 h - to remove one monolayer if the sputter yield is 1, and 4 h if the sputter rate is 10. However, if we are working with polymers we need significantly lower ion doses to remove a monolayer. It is believed [4] that one impact of a primary ion affects an area of about 10 nm2, which is equivalent to a circle of about 3.5 nm diameter. Hence if the sample consists, for example, of a monolayer film of polymer material, a dose of 10n ions/cm2 could in principle be sufficient to remove or alter all material on the surface. With a current density of 1 nA this takes about 1500 s or 25 min only. For adsorbates such as CO adsorbed on a metal surface, we estimate that the monolayer lifetime is at least a factor of 10 higher than that for polymer samples. Thus for static SIMS, one needs primary ion current densities on the order of 1 nA/cm2 or less, and one should be able to collect all spectra of one sample within a quarter of an hour. 

Depth scale calibration of an SIMS depth profile requires the determination of the sputter rate used for the analysis from the crater depth measurement. An analytical technique for depth scale calibration of SIMS depth profiles via an online crater depth measurement was developed by De Chambost and co-workers.103 The authors proposed an in situ crater depth measurement system based on a heterodyne laser interferometer mounted onto the CAMECA IMS Wf instrument. It was demonstrated that crater depths can be measured from the nm to p,m range with accuracy better than 5 % in different matrices whereas the reproducibility was determined as 1 %.103 SIMS depth profiling of CdTe based solar cells (with the CdTe/CdS/TCO structure) is utilized for growing studies of several matrix elements and impurities (Br, F, Na, Si, Sn, In, O, Cl, S and ) on sapphire substrates.104 The Sn02 layer was found to play an important role in preventing the diffusion of indium from the indium containing TCO layer. 

In secondary ion mass spectrometry (SIMS) the sample surface is sputtered by an ion beam and the emitted secondary ions are analyzed by a mass spectrometer (review Ref. [360]). Due to the sputtering process, SIMS is a destructive method. Depending on the sputtering rate we discriminate static and dynamic SIMS. In static SIMS the primary ion dosis is kept below 1012 ions/cm2 to ensure that, on average, every ion hits a fresh surface that has not yet been damaged by the impact of another ion. In dynamic SIMS, multiple layers of molecules are removed at typical sputter rates 0.5 to 5 nm/s. This implies a fast removal of the topmost layers of material but allows quantitative analysis of the elemental composition. 

In this way, the mass of the ions can be deduced from their arrival time at the detector and a complete mass spectrum is acquired for every pulse. Since after each pulse we have to wait until all ions have arrived at the detector, TOF-SIMS is limited to low sputter rates. This does not allow depth profiling, but makes TOF-SIMS virtually non-destructive compared to dynamic SIMS. 

In SIMS a primary ion beam (1-20 keV) causes ejection (sputtering) of neutrals and ions from a solid specimen the secondary ions are mass-analyzed. In static mode, sampling is restricted to the first 1-3 atom layers at the surface by keeping the sputtering rate low (0.1 nm/hour). The ejected ions and ion clusters give information on the nature and may give clues to the chemical state of species present. 

SIMS is used for quantitative depth profile determinations of trace elements in solids. These traces can be impurities or deliberately added elements, such as dopants in semiconductors. Accurate depth prohles require uniform bombardment of the analyzed area and the sputter rate in the material must be determined. The sputter rate is usually determined by physical measurement of the crater depth for multilayered materials, each layer may have a unique sputter rate that must be determined. Depth prohle standards are required. Government standards agencies like NIST have such standard reference materials available for a limited number of applications. For example, SRM depth profile standards of phosphorus in silicon, boron in silicon, and arsenic in silicon are available from NIST for calibration of SIMS instmments. P, As, and B are common dopants in the semiconductor industry and their accurate determination is critical to semiconductor manufacture and quality control. 

For DYNAMIC SIMS, the primary ion current density is increased to > 1 pA/cm so that usually more than one monolayer of material is removed during the analysis. For a microspot analysis, the analyzed and hence bombarded area is restricted (see row 3, Table 1) whereas the high sputter rate necessary for depth profiling is achieved by using a high primary ion current (row ). 

Another potential difficulty with dynamic SIMS is that, in multicomponent systems, various elements may sputter at different rates. This will lead to segregation of the more slowly sputtering component at the surface. At steady state this surface segregation must exactly compensate for the lower sputtering rate, so that the ratio of sputtered ions will accurately reflect the composition of the material, but transient effects will occur before this steady state is reached. This is a problem if one is interested in the composition profile immediately beneath the surface. What can be done is to coat the sample with a thin, sacrificial layer of polymer (typically about 50 nm thick) steady state is then reached by the time etching has reached the sample... 

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