Research Article

Received: 29 June 2010 Revised: 14 August 2010 Accepted: 29 September 2010 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/sia.3708

SIMS depth proling of semiconductor interfaces: Experimental study of depth resolution function
Yu. Kudriavtsev,a S. Gallardo,a O. Koudriavtseva,a A. Escobosa,a V. M. SanchezR,a M. Avendano,a R. Asomozaa and M. Lopez-Lopezb
Reconstruction of original element distribution at semiconductor interfaces using experimental SIMS proles encounters considerable difculties because of the matrix effect, sputtering rate change at the interface, and also a sputtering-induced broadening of original distributions. We performed a detailed depth proling analysis of the Al step-function distribution in GaAs/Alx Ga1x As heterostructures by using Cs+ primary ion beam sputtering and CsM+ cluster ion monitoring (where M is the element of interest) to suppress the matrix effect. The experimental Depth Resolution Function (DRF) was obtained by differentiation of the Al step-function prole and compared with the reference DRF found from depth proling of an Al delta layer. The difference between two experimental DRFs was explained by the sputtering rate change during the interface proling. We experimentally studied the sputtering rate dependence on the Alx Ga1x As layer composition and applied it for a reconstruction of the DRF found by differentiating the Al step-function distribution: the reconstructed and reference DRFs were found to be in good agreement. This conrmed the correctness of the treatment elaborated. Copyright c 2010 John Wiley & Sons, Ltd. Keywords: SIMS; interface; depth proling analysis; sputtering rate; depth resolution

Introduction
The most essential requisite for a quantitative understanding of modern semiconductor heterostructures or for establishing reliable relations between the formation parameters and the characteristic properties of thin semiconductor lms is the knowledge of their compositional structure, in particular, in the interface regions. Special depth proling experimental techniques are essential for acquisition of this information. A record sensitivity and depth resolution are major factors making SIMS one of the prime analytical techniques used for depth proling analysis. At the same time, the use of SIMS for depth proling of complex structures is still limited because of the matrix effect, i.e. a strong dependence of the secondary ion emission on the surface composition. The matrix effect results in a considerable modication of original element distributions during SIMS depth proling analysis and complicates interpretation of experimental proles, especially for interfaces. Experimental sputtering rate change that frequently occurs at the interface between two different materials also complicates data interpretation. In addition, if we remember about spreading of the original element distribution during ion sputtering due to the ion mixing effect and surface relief evolution, it becomes quite clear that reconstruction of original depth proles is an extremely difcult task, if at all possible. All the facts mentioned above are especially important in the case of SIMS depth proling analysis of modern heterostructures, such as quantum wells, delta-doped layers, and multilayers, the characteristic sizes of which are comparable with the characteristic dimension of the component redistribution caused by ion sputtering. A suitable solution of the problem is offered by reconstruction of the original indepth distribution from

experimental proles using the so-called Depth Resolution Function (DRF) determined experimentally or theoretically.[1 3] As a rule, a linear relationship between the secondary ion intensity I(t) measured as a function of time, t, and concentration, C(z), measured as a function of depth, z, is assumed in the dilute impurity limit and for homogeneous matrixes. Provided a stationary situation exists between the surface matrix composition and structure and the impinging primary beam, the signal obtained after erosion to a depth, z, and recorded as a function of time can theoretically be expressed as the convolution integral[1,2]
+

I(z) =

C(z z ) g(z )dz

(1)

where I(z) is the measured and normalized intensity at the sputtered depth, z, C(z) is the normalized true concentration prole of the respective element at depth, z, and g(z) is the normalized DRF for given measurement conditions. According to Eqn (1) we can get experimental DRF in two cases: (i) If the true concentration prole, C(z) is a very thin layer (d 0), the socalled delta layer, with C(z) = 0 in its vicinity. This distribution can be described mathematically by a delta function. Therefore, as it follows from the equation for I(z), the experimental depth prole

Correspondence to: Yu. Kudriavtsev, Dep. Ingeniera Elctrica SEES, CINVESe TAV - IPN, Av. IPN #2508, Mxico, DF. E-mail: yuriyk@cinvestav.mx e

a Dep. Ingeniera Elctrica SEES, CINVESTAV - IPN, Av. IPN #2508, Mxico, DF e e b Dep. Fsica, CINVESTAV- IPN, Av. IPN #2508, Mxico, DF e

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Yu.Kudriavtsev et al. of such a structure is g(z) [1 4] I(z) = g(z) (2)

(ii) If the normalized true concentration prole, C(z) can be tted by a Heaviside function H(z), which is a step-function distribution, C(z) = 1 or 0, and if the sputtering rate, S = dz dt is known and constant, the DRF can be found from the differentiated measured prole[1,3] dI(z) d = ( dz dz
+

H(z z ) g(z )dz ) = g(z)

(3)

where we use the Heaviside function feature: dH(z z ) dz = (z z ). In our study, we examined the applicability of the theoretical approach described above by using specially grown Al delta layers and Al step-function distributions (GaAs/AlGaAs heterostructure). We differentiated experimental Al step-function proles, reconstructed them by taking into account the sputtering rate dependence, and compared with the Al delta layer prole. Their coincidence was the indication of the correctness of the reconstructions made. The nal goal of our study was to develop an experimental technique for reconstruction of original compositions at interfaces of III-V heterostructures from experimental SIMS depth proles for the case when the sputtering rate (S = dz dt) changes in a stepwise fashion at the interface. Since the matrix effect results in the nonlinear relation between the secondary ion intensity, I(t), and concentration, C(z) for ordinary SIMS regimes, we applied the so-called CsM+ mode, i.e. cesium ion beam sputtering of targets with monitoring of secondary CsM+ cluster ions (where M is the element of interest) to minimize the matrix effect. There is vast experimental evidence that the matrix effect is really weak under this regime.[5,6]

Figure 1. SIMS depth distribution of Al in the GaAs/AlGaAs test structures prepared by MBE. (See the sample description in the text).

Experimental
SIMS depth proling was performed with a Cameca IMS-6F ion microprobe. A nely focused cesium ion beam with ion energy of 5 keV and with an angle of incidence of about 45 with respect to the normal, scanned a 300 300 micron crater on the sample surface. The primary ion current was varied from 2 to 20 nA. Secondary CsM+ cluster ions and also Cs2 M+ cluster ions (where M = Al, Ga, As) emitted from the central part of the bombarded area of about 40 microns (the third eld aperture) were analyzed with a double-focusing mass spectrometer and were detected with an Electron Multiplier, or with a Faraday Cup, in accordance with their intensities. Experimental sputtering rates were determined by measuring the experimental crater depths with a Dektak-II proler. The experimental error for the depth measurements did not exceed 5%. Experimental GaAs/Alx Ga1x As heterostructures were grown by Molecular Beam Epitaxy (MBE). We suggested that this technique provides preparation of the interface between a GaAs and AlGaAs layer close to an ideal one and allows one to choose precisely the composition of the Alx Ga1x As layer grown. We prepared three different samples for our study: the rst sample (#1) included 4 Al delta layers separated from each other by about 70 nm of GaAs. The second sample (#2) referred to as a low-step structure; and the third sample (#3) called a high-step structure consisted of

two Alx Ga1x As layers with x = 0.02 and x = 0.64, respectively, separated from each other by about 70 nm of GaAs. The rst Al delta layer and the leading edges of the Al step-function distributions were located about 70 nm below the surface. Depth proling analysis of the low-step heterostructure was assumed to proceed with a constant sputtering rate, whereas the sputtering rate at the GaAs/Al0.64 Ga0.36 As interface during depth proling analysis of the high-step structure was assumed to change in a stepwise fashion. A set of Alx Ga1x As layers with known compositions: x = 0, 0.22, 0.42, 0.56, and 0.64, and with a thickness of about 1 m was grown by MBE for an additional study of secondary ion intensities (matrix effect) and sputtering rate dependences on composition. Composition analysis of the Alx Ga1x As heterolayers was performed by the X-ray diffraction technique with an XPert Pro (Philips) high-resolution diffractometer in the triple-axis 2 mode.

Results and Discussion

Figure 1 shows experimental depth distribution of Al in all three test samples. Note that the dynamic range was wide and the interfaces were abrupt for all three structures, which provided good conditions for the DRF analysis. All the AlGaAs layers in both step-function structures (#2 and #3) were grown with equal thicknesses, so the difference in the sputtering times for the AlGaAs layers observed in Fig. 1 for sample #2 and sample #3 can be explained by different sputtering rates. We discuss below, this effect in detail. First of all, we compared the direct DRF of the Al delta layer (sample #1) and the DRF obtained by differentiating the CsAl+ signal increase at the leading edge of the Al0.02 Ga0.98 As stepfunction layer in sample #2. Figure (2a) shows both dependences normalized to the same intensity scale. It can be seen that these two experimental DRFs are similar. This conrms a negligible matrix effect and a constant sputtering rate at the GaAs/Al0.02 Ga0.98 As interface during the depth proling analysis. At the same time, the derivative of the Al prole at the leading edge of the rst Al0.6 Ga0.4 As layer in sample #3 appears to be
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SIMS depth proling of semiconductor interfaces

(a)

(b)

Figure 2. Comparison of the Al delta-layer distribution in sample #1 and the differentiated Al low-step distribution in sample #2 a); and Al high-step distribution in sample #3 b).

Figure 3. Relative Al ion intensity a); and sputtering rate of Alx Ga1x As solid solutions b); as a function of Alx Ga1x As composition. Al and Ga were monitored as CsM+ and Cs2M+ cluster ions.

essentially thinner than the reference DRF of the delta layer (Fig. (2b)). It was logical to suggest that the matrix effect, or the sputtering rate variation, or both effects, cause the obtained difference between the two experimental DRFs. Therefore, we performed a detailed analysis of relative ion intensities for the monitored ions and experimental sputtering rate of Alx Ga1x As as functions of Al concentration. Depth proling analysis of the reference Alx Ga1x As layers with known compositions was also performed. Figure (3a) shows relative intensities for CsAl+ and Cs2 Al+ cluster ions as a function of relative Al concentration, x. In agreement with the results reported earlier,[6,7] both relative intensities linearly grow with x. But at the same time the relative Cs2 Al+ intensity coincides exactly with the relative aluminum concentrations for all the compounds analyzed (y = x function). This suggests that the matrix effect for the Cs2 M+ secondary ions is negligible, but there is a slight matrix effect for the CsM+ secondary ions. Thus, in the case of depth proling analysis of the GaAs/Alx Ga1x As structure using CsAl+ and CsGa+ cluster ions we should rst recalculate Al and Ga concentrations by using correcting coefcients which can be found by tting experimental points in Fig. (3a).
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The sputtering rates for the Alx Ga1x As epilayers with different Al concentrations were obtained under the experimental regime identical to that used for analysis of the test structures (Fig. 1). Figure (3b) shows the experimental sputtering rates as a function of the layer composition (x). The best tting for the data was found as S(x) = 7 2.5 x, [/sec] (4) Later, we used this equation to reconstruct the experimental Al and Ga depth proles measured for the high-step Al0.6 Ga0.4 As layers. Further, we considered theoretically how the sputtering rate change at the GaAs/AlGaAs interface affects the experimental Al step-function prole. In an idealized case, the sputtering rate changes in a stepwise manner at the GaAs/AlGaAs interface from the sputtering rate of GaAs to the sputtering rate of Alx Ga1x As. In real depth proling analysis the ion mixing effect and surface roughness evolution under ion bombardment lead to a broadening of the elements at the interface and, as a consequence, result a broadening of the step-function dependence for S(t). So, the exact knowledge of the sputtering rate dependence on time S(t) is obviously necessary for a correct transformation of the measured sputter prole into the original indepth distribution.

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Yu.Kudriavtsev et al.

(a)

(b)

Figure 4. Experimental sputtering rate for depth proling analysis of sample #3 as a function of sputtering time. A comparison of the sputtering rate found with Cs2M+ and CsM+ (where M = Al, Ga) cluster ions is presented (Eqns 5 and 6).

After other authors,[1,9] we assumed that there was a direct relation between the sputtering rate and the Alx Ga1x As composition, so the sputtering rate was calculated for any moment of sputtering as (5) S(t) = CGaAs (t) SGaAs + CAlAs (t) SAlAs where Si is the sputtering rate (Eqn 4), and Ci is the relative concentration of GaAs and AlAs phases. Relative concentrations for any point of the experimental prole were calculated as relative intensities of corresponding secondary ions CGaAs (t) IGa (t) IGa (t) + IAl (t) IAl (t) CAlAs (t) IGa (t) + IAl (t) (6a) (6b)
Figure 5. Comparison of the Al delta-layer distribution in sample #1 and differentiated Al high-step distribution in sample #3 found with Cs2M+ cluster ions a); and CsM+ cluster ions b); after normalization to the sputtering rate dependence.

where Ii (t) is the secondary ion intensity of CsM+ (here M is Al or Ga) or Cs2 M+ cluster ions. If Cs2 M+ cluster ions are used, the relative concentration can be found directly from Eqns 6a and 6b; whereas in the case of CsM+ cluster ion monitoring their intensities were corrected in accordance with the tting dependence derived above (Fig. (3a)). Figure 4 shows experimental sputtering rates S(t) as a function of sputtering time for the depth proling analysis of the high-step structure (sample #3) found by the technique described above for both kinds of cluster ions. The sputtering rates were normalized to the sputtering rate of GaAs. A slight difference between the sputtering rates for Cs2 M+ and CsM+ ions is discussed below. The experimental SIMS depth prole represents the ion intensity as a function of sputtering time. In order to apply the above described mathematical conversion to experimental SIMS proles of our step-function structures (Eqn 3), we should recalculate the sputtering time into the depth, and the ion intensity into the concentration. If we consider the matrix-effect free analysis, we can use the ion intensities instead of concentrations in Eqn 3 with an accuracy of a constant factor. However, as we have revealed, the depth is not a linear function of the sputtering time for GaAs/AlGaAs depth proling analysis. Therefore, Eqn 3 should be modied. Despite the signicance of the problem, we did not

nd in the literature any mathematical treatment for this case. In our study, we applied the rule of a complex function derivative[8] to differentiate the experimental element prole and found that dI(z(t)) dI dz dI dI = /S(t) = = g(z). dt dz dt dt dz (7)

Thus, the DRF for the step-function distribution in sample #3 can be obtained by normalization of the differentiated experimental Al prole to the experimental sputtering rate S(t). Figure (5a) shows comparison between the Al delta-layer distribution in sample#1 and derivative of the high-step Al distribution in sample #3 measured as Cs2 Al+ cluster ions normalized to S(t). Taking into account the experimental error for the ion intensity monitoring (of about 5%) and the experimental error of the crater measurements (about 5%), we can conclude that these two distributions are in good agreement. This conrms the validity of the suggestions and mathematical treatments made above. In dealing with the experimental depth prole of the highstep structure measured with CsAl+ cluster ions we rst made
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SIMS depth proling of semiconductor interfaces corrections of the ion intensities by taking into account the CsAl+ and CsGa+ signal dependences on the Al concentration (Fig. (3a)). Figure (5b) compares the Al delta-layer distribution and the derivative of Al distribution (corrected) at the GaAs/Al0.6 Ga0.4 As interface measured with CsAl+ cluster ions normalized to S(t). It can be seen that these two distributions differ appreciably. This suggests that a considerable matrix effect existed for CsAl+ and CsGa+ ion emission, which modied the original Al distribution during depth proling analysis of the GaAs/Al0.6 Ga0.4 As heterostructure for low Al concentrations (0.02 < x < 0.2) and for high Al concentrations (0.6 < x < 1). These concentration ranges were not examined in detail in our study, but, as one can see from Fig. 4, the sputtering rates derived from Cs2 M+ and CsM+ ion cluster intensities for these Al concentrations differ remarkably (Fig. (3b)). It should be reminded here that the experimental sputtering rate was calculated with CsAl+ and CsGa+ ion intensities (Eqns 5 and 6). found and the derivate of the SIMS depth prole of the stepfunction distribution should be normalized to this sputtering rate. As the next step in our investigations, we are going to perform a detailed analysis of the matrix effect for the monitored secondary ions and develop a universal technique for reconstruction of the original indepth distribution at any interface for the case when both the matrix effect and the sputtering rate change take place during depth proling analysis.

References
[1] A. Benninghoven, F. G. Rudenauer, H. W. Werner, in Secondary Ion Mass Spectrometry Basic Concepts, Instrumental Aspects, Applications and Trends, Wiley: New York, 1987, p. 310. [2] S. Hofmann, Rep. Prog. Phys. 1998, 61, 827. [3] S. Hofmann, J. Vac. Sci. Technol. 1991, A9, 1466. [4] T. Kitada, T. Harada, S. Tanuma, Appl. Surf. Sci. 1996, V.100/101, 89. [5] Y. Gao, J. Appl. Phys. 1988, 64, 3760. [6] M. Haag, H. Gnaser, H. Oechsner, in Secondary Ion Mass Spectrometry SIMS IX, Proceedings of the 9-th Int. Conference on Secondary Ion Mass Spectrometry, Yokohama, 712 Nov., Japan, Wiley: Chichester, 1993, pp. 390393. [7] Y. Yoshioka, D. Komyoji, F. Tohjou, T. Matsunaga, K. Tsukamoto, in Secondary Ion Mass Spectrometry SIMS IX, Proceedings of the 9-th Int. Conference on Secondary Ion Mass Spectrometry, Yokohama, 712 Nov., Japan, Wiley: Chichester, 1993, pp. 377381. [8] G. A. Korn, T. M. Korn, in Mathematical handbook for scientists and engineers: denitions, theorems and formulas for reference and review, (2nd edn), Dover Publications, Inc.: New York, 2000, p. 192. [9] P. C. Zalm, Rep. Prog. Phys. 1995, 58, 1321.

Conclusion
Summarizing, the CsM+ mode with secondary Cs2 M+ cluster ion monitoring can be used for the matrix effect-free depth proling analysis of III-V compound semiconductors. CsM+ cluster ion emission from Alx Ga1x As solid solutions has been found to be accompanied by an appreciable matrix effect. Additional studies of the matrix dependence should be carried out to clarify the situation and nd the true matrix dependence for these ion yields. Atomically sharp interfaces can be used for experimental acquisition of the DRF by the matrix effect-free SIMS depth proling analysis. To this end, the experimental sputtering rate should be

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