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Applied Surface Science 255 (2008) 877879

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Critical distance for secondary ion formation: Experimental SIMS measurements

Y. Kudriavtsev *, S. Gallardo, A. Villegas, G. Ramirez, R. Asomoza
ctrica-SEES, CINVESTAV-IPN, Col. San Pedro Zacatenco, Mexico DF 07360, Mexico Dep. Ingeniera Ele

A R T I C L E I N F O

A B S T R A C T

Article history: Available online 8 May 2008 Keywords: Ion sputtering Energy distribution SIMS Ionization critical distance

We have performed direct experimental measurements of the critical distance for the secondary ion formation process. To this end, we compared the experimentally measured energy distribution of secondary Si ions with the theoretical energy distribution (Sigmund-Thompson relation) of secondary Si atoms. Our model states that the maxima positions of these two energy distributions differ by the Coulomb interaction potential between the outgoing ion (Si in our case) and a charge with the opposite polarity formed at the surface after electron transition between the outgoing Si atom and the surface. Quite a reasonable value was obtained for the critical distance, but with a large scatter in experimental data. The conclusion has been made that the experimental technique should be improved to get more precise values of the critical distance, which is of high importance for practical purposes. 2008 Elsevier B.V. All rights reserved.

1. Introduction Many models of secondary ion formation consider the so-called critical distance for the ionization process. At this distance the electron transition between the outgoing particle and the emitting surface becomes negligible. Only qualitative estimates of the critical distance are available in the literature; it is estimated to be in the range from 4 to 10 A by different authors [1]. This work is a logical continuation of our previous study [2,3] where we investigated the ionization probability (IP), positive and negative, of secondary Si atoms as a function of atom energy. The IP dependences found experimentally are very similar to those published in the literature [47]. On the other hand, these dependences cannot be explained by any existing ionization model. We compared our data with the predictions of the most popular Electron Tunneling model [8] and found that only the secondary ions sputtered with the energy higher than approximately 20 eV follow the predictions of the model. Therefore, we tried to nd another explanation of the IPs. Like in [7], we considered the existence of two different ionization mechanisms for secondary atoms. The low-energy atoms (<20 eV) are ionized due to surface excitation (adiabatic ionization), whereas the highenergy atoms (>30 eV) are ionized due to electron tunneling (non-adiabatic ionization). This consideration explained reason-

ably the experimental negative Si ion yield [2]. However, one fact remained highly doubtful. We assumed that the atom energy of about 20 eV is a boundary between the adiabatic and nonadiabatic ionization processes in the case of Si atoms sputtered by a cesium ion beam [2]. This value depends on the time of ight of sputtered atoms through the near-surface layer, where intense electron transitions between the atoms and the surface happen. It is evident that these time intervals and, hence, boundary energies differ for different atoms because of their mass differences. We mean the well known relation between the time of passage (tc), energy (E), velocity (yM) and mass (M) of a sputtered p p atom: t c xc =yM xc M= 2E. Contrary to our expectations, very similar behaviors of ion yields for atoms with relatively large mass differences (Si [2,3,7], Cu, Cr, Zr, Ag [4], In [5], Zn, Cu, Ni [6]) were found. To resolve this discrepancy, we looked for another explanation of the experimental energy dependences of the IP. We considered the secondary ion formation process and interaction of the ion just formed and the surface in detail [3] and put forward the hypothesis that formation of a local surface charge resulted from the electron transition between an outgoing particle and the surface. This surface charge forms a potential barrier to the outgoing ions just formed and modies their trajectory and energy distribution, especially for low-energy sputtered particles. The energy distribution of secondary ions was found [3] to be NEi dEi Ei Ei U Eq 3 cos #i dEi ; (1)

* Corresponding author. E-mail address: yuriyk@cinvestav.mx (Y. Kudriavtsev). 0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.05.064

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where U is the surface binding energy of sputtered particles, ui is the angle of ion emission with respect to the surface normal (differing from the initial atom emission angle [3]), and Eq is the Coulomb interaction potential between the outgoing ion and the surface charge at the critical distance of ion formation xc Eq e2 2 xc (2)

where e is the electron charge. Using the well known Sigmund-Thompson relation for the energy distribution of sputtered atoms and Eq. (1), the ion yield for the particles sputtered close to the surface normal was found [3] to be Ye de e U3 e U Eq 3 de; (3)

Fig. 2. Angular distribution of Si atoms sputtered from Si by a cesium ion beam with energy 14.5 keV and angle of incidence 248 calculated by TRIM code.

It demonstrated quite a good agreement with our experimental data [2,3], as well as with other experimental dependences given in the literature. Fig. 1 shows, as an example, the ion yield for the In particles sputtered from Indium by Ar ions calculated from Eq. (3). We used the following values to perform calculations: U = 2.5 eV, xc % 2ra % 4 A (where ra is the In atomic radius). There is a good agreement between this dependence and the experimental dependence found by Mazarov and co-workers (see Fig. 3a in [5]). According to Eq. (1), the maximum of the ion energy distribution is at (Eq + U)/2, irrespective of the ion emission angle. This value is higher than the maximum of the energy distribution of the same atoms dened according to the Zigmund-Thompson model as U/2 [9]. Thus, comparison of these two maxima, found experimentally (the best way) or theoretically (in the case of atom energy distribution), allowed us to dene from Eq. (2) the critical distance for secondary ion formation. In this study we measured the energy distribution of the secondary Si ions sputtered from silicon by a cesium ion beam, compared its maximum with the Si sublimation energy (U = 4.7 eV), and calculated the critical distance for Si formation. 2. Experimental The experimental part of the study involved the use of a Cameca IMS 6f instrument. A cesium ion beam with energy of 15 keV and

Fig. 1. Theoretical secondary ion yield of In atoms sputtered from In by Ar+ ions as a function of atom inverse velocity.

with an ion current of about 20 nA scanned a 200 mm raster. The secondary ions emitted from a central surface area of about 150 mm (the rst eld aperture) were monitored with a double focusing mass spectrometer. Due to the geometrical conguration of ion optics in the 4f7f instruments, the secondary ions emitted close to the surface normal are effectively focused and then monitored. A TRIM code simulation has demonstrated (see Fig. 2) that most of the sputtered Si atoms in our experiments are emitted close to the surface normal, too. Generally speaking, the ionization of sputtered atoms can depend on the emission angle, especially for low-energy atoms. In order to avoid such a dependence, or at least radically minimize it, we restricted ourselves to analyzing only the secondary ions emitted close to the surface normal. To this end, we performed our measurements with the third Contrast Aperture (60 mm). Using this contrast aperture, 1 mm lateral resolution can be obtained in the microscope mode of a Cameca 6f instrument, which means that only the ions ejected into a small solid angle respect to the normile are detected. A Si wafer with the (1 1 1) orientation and a surface resistance of 0.001 V/cm2 grown by the Czochralski technique was used in this study as an experimental sample. The initial Si surface was pre-sputtered during 23 min in order to remove a native oxide. The energy distributions of H (see comments below) and Si ions were obtained by the standard method described in [10], i.e., by measuring the secondary ion current and simultaneously varying the voltage offset applied to the sample potential (5 keV), while optical elements of the secondary ion beam line being kept unchanged. The energy bandwidth of the energy window of the mass spectrometer was amounted to approximately 23 eV during the measurements. It is a commonly encountered problem to dene the energy scale zero for the ion energy distribution measured by using the scheme described above. In this study we dened the zero by a linear extrapolation of the leading edge of the energy distribution of secondary H ions. The H concentration in Czochralski Si found in our previous work to be as high as 1017 atoms/cm3 provides a high enough signal for the experimental H energy distribution. Because of a large mass difference between H and Cs, and Si their collisions are accompanied by transfer of a low energy to H. The surface binding energy of hydrogen U(H) = 5.7 eV [11] is higher than that of Si, so the emitting surface should be enriched with H in comparison with its bulk concentration. For the same reasons, we concluded in [12] that the H ions sputtered predominantly from the top monatomic layer have a relatively low energy. On the other hand, secondary H ions are in a sufciently high quantity to give a good statistics

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distance exceeds the double atomic radius by a factor of 1.5, which looks quite reasonable. It is interesting to note that the silicon xc found coincides with the so-called electrical radius of a Si atom (re) dened as a cubic root of the Si atom polarizability: a(Si) = 5.38 A3 [15]. Double re amounts exactly to 3.5 A. The physical meaning of re can be dened as the maximal separation between the outermost electron and the effective nuclear charge used for denition of the elemental electronegativity in some empirical models. 4. Conclusion Thus, we have found that the experimental critical distance for secondary Si ion formation during cesium ion sputtering of silicon reaches xc = 3.5 0.9 A, which looks quite a reasonable value. Note that this magnitude of xc is essentially lower than that used by the SIMS community earlier (10 A). Improvements of the experimental technique are highly necessary to get more precise values of xc and also to measure xc for other elements and matrixes. A perfect experiment should include measurements of the energy distribution of sputtered ions and atoms performed under the same instrument setup. This will provide correct measurements of the surface binding energy for the element analyzed and make it possible to avoid any instrument transmission dependences. An inert gas ion beam looks preferable for such measurements in order to minimize the changes in a surface composition and work function caused by ion sputtering. Acknowledgment

Fig. 3. Energy distributions of Si atoms (theory) and ions (experiment). The inset shows experimental energy distribution of Si and H secondary ions used to nd the zero of the energy scale.

for the energy range of 03 eV (see below). Therefore, a linear extrapolation of the H energy distribution to crossing with the energy scale should gives, in our opinion, a more accurate zero for the energy scale. 3. Experimental results and discussion Fig. 3 shows the energy distribution of the Si ions sputtered from Si by a 15-keV cesium ion beam. The energy scale in this gure has already been corrected for the zero energy scale position found by a linear extrapolation of the leading edge of the H energy distribution (see the inset in this gure). To get a good statistics for the values measured, we repeated the same alignment and instrumental setup many times during a month. Rather poor reproducibility was obtained for the maximum position of the Si energy distribution found by using the scheme described above. Finally we estimated the critical distance to be 3.5 0.9 A. A large scatter in the experimental data is obvious. In our opinion, the main reason of such a high experimental error is a poor statistics for the secondary ions sputtered with an energy of 03 eV. Another possible source of the experimental error is an incorrect value of the surface binding energy. Indeed, cesium ion sputtering of Si leads to formation of a SiCs compound. We estimated the cesium surface concentration to be as high as 15 at.% for the experimental regime used here [13]. It is reasonable to suppose that the Si surface binding energy in this case and the silicon sublimation energy used for our calculations considerably differ. It is interesting to compare the critical distance obtained here with the characteristic Si radii: covalent radiusrcov(Si) = 1.11 A and atomic radiusra(Si) = 1.11 A [14]. The experimental critical

This work was partially supported by CONACYT (Grant 48454). References

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