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NIM B
Beam Interactions with Materials & Atoms

Nuclear Instruments and Methods in Physics Research B 266 (2008) 35403544 www.elsevier.com/locate/nimb

Collision cascade temperature

Yuriy Kudriavtsev *, Rene Asomoza
Dep. Ingeniera Electrica-SEES, CINVESTAV-IPN, Av. IPN #2508, San Pedro Zacatenco, Mexico D.F. 07360, Mexico Received 29 March 2008 Available online 8 June 2008

Abstract Interaction of a projectile with a solid has been considered in detail. It has been found that any collision cascade generated by a projectile can be characterized by the average kinetic energy of cascade atoms that represents an instantaneous temperature of the cascade during its very short lifetime (1012 s). We refer to this value as the dynamic temperature in order to emphasize the fact that cascade atoms are in a dynamic equilibrium and have a denite energy distribution. The dynamic temperature denes the electron distribution in the cascade area and, hence, the ionization probability of sputtered atoms. The energy distribution of cascade atoms and, as a consequence, the dynamic temperature can be found experimentally by measuring the energy distribution of sputtered atoms. The calculated dynamic temperature has been found to be in good agreement with the experimental data on ion formation in the case of cesium and oxygen ion sputtering of silicon. Based on the developed model we suggest an experimental technique for a radical improvement of the existing cascade sputtering models. 2008 Elsevier B.V. All rights reserved.
PACS: 34.50.Bw; 79.20.Rf; 79.20.Ap; 82.80.Ms Keywords: Temperature; Ion sputtering; Collision cascade; SIMS

1. Introduction Penetration of an energetic ion into a solid generates a cascade of ionatom and atomatom collisions. As a result, some atoms from the top mono-atomic layer can leave the surface as neutral or charged particles. The ionization probability of such sputtered particles is of great practical interest because of the fact that secondary ions form a basis for Secondary Ion Mass Spectrometry (SIMS) widely used for surface analysis. In 1963 Dobretsov suggested the so-called Statistical Model [1]. The model considers ion formation from a secondary atom sputtered from a collision cascade area at a critical distance xc from the surface. At shorter distances from the surface (xc) the electrons of outgoing atoms and the electrons of the solid form a common electronic system with the electron distribution over energetic levels obeying
*

the FermiDirac statistics. The ionization probability P in the model [1] exponentially depends on the dierence between the work function (W) of the surface analyzed and the ionization potential (I ) and electron anity (A ) e p of the outgoing particles at the critical distance for positive and negative ions, respectively     Ip W W A e P / exp ; P / exp ; 1 k Tc k Tc where k is the Boltzmann constant; and Tc is the temperature in the cascade area. Dobretsov and his followers did not suggest any relation for the cascade temperature in spite of its key role in this model. Some other models collected into the group called local thermodynamic equilibrium models (LTE) [24] postulate the existence of a hot local plasma, which is in a thermodynamic equilibrium, and give the formulas for ionization of the atoms sputtered from this plasma very similar to Eq. (1). Fitting of Eq. (1) and similar expressions to experimental data yields quite high temperatures ranging from

Corresponding author. Tel.: +52 55 57473800. E-mail address: yuriyk@cinvestav.mx (Y. Kudriavtsev).

0168-583X/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.nimb.2008.05.125

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2000 K to 8000 K [4] depending on the sputtering regime. This temperature range was not conrmed by direct temperature measurements for the samples under ion bombardment [4]. In this paper we introduce a new notion, i.e. the instantaneous temperature, to characterize the energetics of a short-lived state of an atomic system and consider a simple method for calculation of such a temperature in the case of collision cascades. In our opinion, average kinetic energy of atoms in the cascade area (phonon sub-system) denes completely this temperature, as well as the quasi-equilibrium electron distribution in the collision cascade area and, hence, determines the ionization of secondary particles sputtered from the solid. Note that we suggest improvements for the Statistical model of ion formation rather than the LTE models. Below we discuss a radical dierence between the Statistical and LTE models. 2. Theoretical consideration of the collision cascade temperature First of all we consider in detail the features of the collision cascades caused by projectiles in the near-surface layer of a solid. The main phenomenon under consideration is stopping of a primary ion in a limited solid volume and transfer of its initial energy to atoms in this volume. Generally speaking, the energy of solid atoms and, hence, the temperature of the solid is mainly determined by the kinetic energy of the atoms which oscillate around their equilibrium positions. When a projectile initiates collisions in a solid, the energy of the ion is transferred mainly to the nuclei of target atoms (the so-called nuclear stopping power) and only a small part of it is transferred to electrons because of a great dierence in masses between them. Note that we discuss low-energy ion bombardment (ion energy of 110 keV) typical of modern SIMS instruments. The transferred energy increases the kinetic energy of target atoms: their oscillation amplitude increases, and if the transferred energy exceeds the so-called displacement energy barrier (Edis), the atom can leave its crystal site position and move through the crystal. This motion is accompanied by atom collisions with other solid atoms. The recoil movement stops when its kinetic energy becomes lower than Edis. A number of such recoils form a collision cascade. Let us compare collision cascades with any other atomic system. First of all, we consider the time scale of ion sputtering and ionization processes. Starting with penetration of a projectile, the number of recoils increases rapidly during approximately 1013 s [5] and reaches a at maximum. Then the number of collisions decreases at approximately the same rate as at the growth stage. The full collision cascade lifetime can be estimated after [5] to be as low as 1012 s. This time is essentially longer than a typical electron transition time (about 1015 s), so at any moment of lifetime of the collision cascade we have a strictly dened electron distribution in the cascade area. This electron dis-

tribution is determined by the atom energy distribution because of a great dierence (about three orders of magnitude) between the heat capacities of the phonon and electron sub-systems of a solid. As the second step, we consider a spatial limitation of any collision cascade. All theoretical models consider the displacement energy (Edis) in the range 1525 eV, depending on the target [6]. During a single act of ion-atom interaction a projectile can transfer to a solid atom the energy that varies from zero to the maximal transferable energy Emax Emax 4 M1 M2 M 1 M 2
2

Eo c Eo ;

where M1 and M2 are the masses of the primary ion and atom of the solid, respectively. The existing theoretical model predicts the power-like dependence for the energy distribution of recoils [7] f E / E
2m

where m is the parameter that depends on the energy of primary ions. It is clear from Eq. (3) that an essential part of interactions is accompanied by a transfer of a too small fraction of energy (less than Edis), so the recoil cannot leave their initial positions. However, some target atoms receive enough energy to leave their sites. The average recoil displacement hqi can be estimated from the recoil energy distribution (Eq. (3)). First, the range of the primary recoils can be found as Z de qe % 1:33 e0:5 : 4 sn e Here we use the low-energy approximation of Yudins formula [8] for the nuclear stopping power sn e 3 e0:5 = 2 eje(1 % 1:5 e0:5 and neglect the electron stopping power to simplify the calculations. Then the average displacement is calculated by integrating q(e) over the recoil energy distribution from edis to ceo  Z ceo Z ceo hqi qe f e de f e de % 2:667 e0:5 : 5 dis
edis edis

The calculations for a typical experimental regime, i.e. cesium ion sputtering of silicon (the displacement barrier for Si is 15 eV [6]) with an ion energy of 14.5 keV, give the value of about 1.4 nm, or only 56 interatomic distances. This value is essentially lower than the cascade length which is about 28 nm if one estimates it (using TRIM) as the double projected range of a Cs ion in Si. These mean that any collision cascade can be limited, in the rst approximation, by the projectile trajectory. The displacement energy is essentially higher than the kinetic energy of an atom in the original crystal (kT or $0.026 eV at room temperature), and therefore we can conclude that the collision cascade area has quite abrupt boundaries. The next important question we consider here is: what is the charge state of recoils? Unfortunately, we cannot determine it experimentally, and there are no theoretical

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estimates of the charge state for the case of low-energy ion sputtering considered here. We believe that recoils move as dipoles. This happens, in our opinion, because of a shift between positively charged nuclei of the recoil atoms that obtain the greatest fraction of the transferred energy from the projectile during a collision act and negatively charged electronic clouds of the atoms that strongly interact with the nuclei and electronic clouds of neighboring atoms at the moment of the ion-atom interaction. The dipole moment of the recoil can vary because of a periodic character of electric potentials in a crystal. Such recoils-dipoles excite the electronic subsystem of the surrounding solid volume during their movement by passing energy to it. Finally, the initial primary ion energy is dissipated by the electrons of the solid. As mentioned above, the recoil energy distribution can be dened as $E2 [7]. The experimentally measured energy distributions of sputtered atoms conrm the theoretical estimate [7,9]. The fact of the existence of a strictly dened and reproducible recoil energy distribution conrms, by itself, the existence of a dynamic equilibrium for the recoils. The lifetime of any cascade is essentially longer than the sputtering time or the time of passage of a secondary particle through a near-surface layer (10131014 s, depending on the mass and energy of sputtered particles), and therefore the sputtered atoms are ejected from the solid volume where atoms are in a dynamic equilibrium. We have summarized all specic characteristics of collision cascades. They are as follows: Cascade atoms are very close to each other; dierent quantum eects should be considered as for the solid state. An essential fraction of atoms in the cascade area is in movement (of course, during the cascade lifetime). Any cascade exists during a very short time of about 1012 s. In spite of this fact we believe that there is a dynamic equilibrium for the cascade atoms during this lifetime. The charge state of cascade atoms cannot be dened exactly, but in any case they do not form free ions and electrons and, therefore, a collision cascade does not represent plasma. The last conclusion demonstrates a radical dierence between the model we consider and the LTE models of the secondary ion formation process: the LTE models regard any cascade area as hot plasma under a thermodynamic equilibrium. Here we follow the philosophy of the Statistical model that does not consider any plasma. Thus we can conclude that any collision cascade area represents quite a specic system of atoms, or just a specic state of matter, that exists during a very short time as a quasi-isolated system of the atoms that are in a dynamic equilibrium and have a characteristic energy distribution. As mentioned above, the average kinetic energy of atoms in a solid denes the temperature of the solid. So this sug-

gests that the average kinetic energy of recoil atoms kT d % hEc i denes the energetics of the collision cascade, or its temperature. We refer to this temperature as the dynamic temperature (Td) to emphasize its special character. The term temperature used here requires a separate discussion. The notion of temperature is widely used in thermodynamics and many other areas of physics to characterize the average energy of particles in the multi-particle system that is in an equilibrium (or quasi-equilibrium) with the environment. It is believed that the temperature notion cannot be applied to very fast processes, such as collision cascades. It was stated above that there is a denite recoil energy distribution in any collision cascade, which conrms the existence of a dynamic equilibrium in the cascade area. Now we would like to introduce the criterion that species, in our opinion, the limits for the use of the notion of temperature for any short-lived process: the time of temperature measurement of any system in a dynamic equilibrium should be essentially shorter than the duration of this equilibrium. Any collision cascade obeys this criterion. Indeed, we make measurements of the cascade temperature by means of sputtered atoms. The act of sputtering is 10100 times faster than the duration of a dynamic equilibrium of cascade atoms. Thus the emission energy of secondary atoms is determined by an instantaneous energy distribution of cascade atoms, or by an instantaneous cascade temperature. Here a very important remark concerning the statistical approach used should be made. It is obvious that we cannot make any statistical estimation for an individual cascade because of a limited number of recoils in it (a hundred recoils for the typical regime). However, in practice we deal with dierent characteristics of sputtered particles (sputtering yield, energy distribution, ionization probability, etc.) summarized over a great number of dierent cascades. Under the typical experimental SIMS regime the ion current density reaches j = 160 lA/cm2, which means that about 1015 cascades are generated by the primary ions per second and per square centimeter. Now the average kinetic energy of recoils in the collision cascade area can be found from the energy distribution of the recoils f(e) as R Emax e f e de E hEc i Rminmax ; 6 E f e de Emin where Emax and Emin are the maximal (see Eq. (2)) and minimal energy of the recoil atoms. The minimal atom energy corresponds to the atom at rest (the atom does not participate in any collision) and equals kT, where T is the sample temperature. In the rst approximation m in Eq. (2) can be neglected, and after trivial calculations we can nd the average kinetic energy from Eq. (3) with m = 0 as   c Eo hEc i kT ln ; 7 kT

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To simplify Eq. (7), we used the fact that Emax ) kT. Indeed, kT for the ambient temperature reaches 0.026 eV (300 K), whereas Emax reaches thousands of eV. Under the typical sputtering regime the sample temperature increases only slightly; this growth can be neglected in our case in comparison with the upper limit of integral (Emax). For the experimental sputtering regime mentioned above (14.5 keV cesium ion sputtering of Si at room temperature), Eq. (7) yields the average energy as high as hEci = 0.33 eV, which corresponds to the dynamic temperature of Td = 3800 K. Below we compare this kTd with the existing experimental data. 3. Experimental study of the cascade temperature A great advantage oered by the mass-spectrometry SIMS and SNMS techniques is that the recoil energy distribution in any collision cascade can easily be obtained experimentally by using these techniques. The highenergy tail (>20 eV) of the energy distribution of sputtered atoms (SNMS) reproduces the energy distribution of recoil atoms in the collision cascade. The emitting surface represents, in the rst approximation, a at potential barrier with a height of 27 eV, depending on the matrix, for a ux of the recoils moving from the cascade to the surface. This barrier modies the energy distribution for the low-energy recoils (020 eV) alone. So direct SNMS measurements of the energy distribution of sputtered atoms de-convolved with the so-called instrument transmission function (determined by the instrument used) and subsequent calculations of the average kinetic energy (see Eq. (6)) yield the dynamic temperature for the specied ion bombardment regime. In the case of secondary ions (SIMS technique) such calculations are more complicated because the ionization probability of sputtered atoms can depend on the atom energy. Such dependence leads to the modication of the original recoil energy distribution. In this work we used another way to compare the theoretically estimated dynamic temperature with the experimental one for the specied experimental regimes (14.5 keV cesium ion sputtering and 8 keV oxygen ion sputtering of Si). We used for this the relative sensitivity factors (RSFs) acquired experimentally (SIMS) for implanted Si standards [10]. According to Eq. (1), the RSF for element X can be obtained for positive and negative ions as   Ae X Ae Si RSF X % 5 1022 exp ; 8a kT d   I p Si I p X RSF X % 5 1022 exp ; 8b kT d where 5 1022 atoms/cm3 represents the atomic concentration of Si, and the dynamic temperature is 0.33 eV (kT ) d for cesium ion sputtering and 0.312 eV (kT ) for oxygen d ion sputtering. Note that we neglected the pre-exponential factor in our calculations here. It is obvious from Eqs. (8) that the dynamic temperature can be estimated from the

slope of the curve tting the experimental RSFs in the semi-log scale. Fig. 1(a) and (b) shows the experimental RSFs [10] and their ttings with the dynamic temperatures calculated above (see the solid lines in the gures). We believe that the observed deviations of the experimental data from the theoretical curves can be explained by changes in the electron anity (EA) and ionization potential (IP) of the elements located at the critical distance from the surface [1]. Additional studies are needed to resolve this problem. In the case of negative secondary ions sputtered from Si by cesium ions we have demonstrated in Fig. 1(a) RSFs for the elements with the electron anity less than 2 eV. As it was demonstrated in [11], the ionization probability becomes independent of the electron anity for the elements with Ae higher than 1.6 eV. A reasonable correlation between experimental data and their tting for both sputtering regimes is evident. However, an essentially better correlation can be obtained if we assume that the energy distribution of recoil atoms diers a little from that

Fig. 1. Experimental SIMS RSFs obtained for dierent elements implanted in Si [10] under cesium ion beam sputtering with an energy of 14.5 keV (a) and oxygen ion beam sputtering with an energy of 8 keV (b).

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of sputtered atoms represent another way to get the same improvement if the SNMS technique is available. 4. Conclusions Thus, we have introduced the notion of a special dynamic temperature for a collision cascade area. The dynamic temperature is completely dened by the average kinetic energy of atoms in this area and can easily be found experimentally by measuring the energy distribution of sputtered atoms. This temperature characterizes the energy distribution in the electronic subsystem in the cascade area during a very short cascade lifetime (of the order of 1012 s) and, hence, denes the probability of secondary ion formation for a sputtered atom. The comparison between experimental SIMS RSFs and estimated dynamic temperature has led to the conclusion that seems to be very interesting for the SIMS application: we can appreciably decrease the total spread of the RSFs values by increasing the dynamic temperature (compare the solid and dashed curves in Fig. 1(a) and (b)). This can provide a better quantication of SIMS data. Acknowledgment The work was partially supported by Conacyt, Mexico (Grant 48454). References
[1] L.N. Dobretsov, Electron and Ion Emission, NASA Techn. Transl. 1963. [2] C.A. Andersen, J.R. Hinthorne, Science 1975 (1972) 853. [3] C.A. Andersen, J.R. Hinthorne, Anal. Chem. 45 (1973) 1421. [4] A. Benninghoven, R.G. Rudenauer, H.W. Werner, Secondary Ion Mass. Spectrometry Basic, Concepts Instrumental, Aspects, Application and Trends, John Wiley & Sons, 1987, 310. [5] M.W. Thompson, Defects and Radiation Damage in Metals, Cambridge University Press, Cambridge, England, 1969 (Chapter 5). [6] W. Eckstein, Computer Simulation of IonSolid Interactions, Springer Series in Materials Science, Vol. 10, Springer, Berlin, 1991. [7] M.W. Thompson, Philos. Mag. 18 (1968) 377. [8] V.V. Yudin, Soviet physics Doklady 17 (1973) 1076. [9] W.O. Hofer, in: R. Behrisch, K. Wittmaack (Eds.), Sputtering by Particle Bombardment III, Topics in Applied Physics, Vol. 64, Springer-Verlag, 1991. [10] R.G. Wilson, F.A. Stevie, C.W. Magee, Secondary Ion Mass Spectrometry, A Practical Handbook for Depth Proling and Bulk Impurity Analysis, Wiley, 1989, p. 543. [11] Y. Kudriatsev, A. Villegas, S. Gallardo, R. Asomoza, Appl. Surf. Sci. 254 (2008) 2059.

Fig. 2. Collision cascade temperature as a function of power b of powerlike energy distribution ($Eb) of collision atoms. The line is shown to guide the eyes.

predicted by Eq. (3). The best tting was found for the recoil energy distribution $E2.2 (or kTd % 0.156 eV) in the case of cesium ion sputtering and $E1.8 (or kTd % 0.657 eV) in the case of oxygen sputtering (see Fig. 1(a) and (b), dashed curves). The theoretical power (b = 2) is a result of application of the power-like interaction potential for the atom collision description, but its exact form has yet to be proved. The comparison of two sputtering regimes, made above, has revealed dierent dynamic temperatures for dierent ion sputtering regimes. This happens, in our opinion, because of dierent interaction potentials between dierent pairs of particles in collision cascades (projectile-atom and atom-atom). The dynamic temperature dependence on the power b in the case of oxygen 8 keV ion sputtering is schematically demonstrated in Fig. 2. Based on the last conclusion and previous speculations, we suggested the experimental method for a radical improvement of the collision cascade model. The scheme of such an experiment includes SIMS measurements of the dynamic temperature (see the technique described above) and determination of the energy distribution of cascade atoms (using the kTd = f(b) dependence, presented in Fig. 2), after which the initial interaction potential between collision atoms can be de-convolved. A repeated use of this procedure for dierent sputtering regimes provides complete information on the atom interaction in collision cascades necessary for improvement of the cascade theory. Of course, experimentally measured energy distributions