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# Variance of the decay intensity of superdeformed bandsSupported by FAPESP.

## 1 Introduction

The intensity of the collective $`\gamma `$–rays emitted during the cascade down a superdeformed (SD) band remains constant until a certain spin is reached where-after it drops to zero within a few transitions. The sharp drop in intensity is believed to arise from mixing of the SD states with normally deformed (ND) states of identical spin . The model of Refs.  attributes the suddenness of the decay-out to the spin dependence of the barrier separating the SD and ND minima of the deformation potential. Refs.  discuss the effect of the chaoticity of the ND states on the decay-out.

In the present paper we present analytic formulae for the energy average (including the energy average of the fluctuation contribution) and variance of the intraband decay intensity of a superdeformed band in terms of variables which usefully describe the decay-out . In agreement with Gu and Weidenmüller  (GW) we find that average of the total intraband decay intensity can be written as a function of the dimensionless variables $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S`$ and $`\mathrm{\Gamma }_N/d`$ where $`\mathrm{\Gamma }^{}`$ is the spreading width for the mixing of an SD state with ND states of the same spin, $`d`$ is the mean level spacing of the latter and $`\mathrm{\Gamma }_S`$ $`(\mathrm{\Gamma }_N)`$ are the electromagnetic decay widths of the SD (ND) states. Our formula for the variance of the total intraband decay intensity, in addition to the two dimensionless variables just mentioned, depends on the dimensionless variable $`\mathrm{\Gamma }_N/(\mathrm{\Gamma }_S+\mathrm{\Gamma }^{})`$.

## 2 Energy average and variance of the decay intensity

The total intraband decay intensity has the form

$$I_{\mathrm{in}}=\left(2\pi \mathrm{\Gamma }_S\right)^1_{\mathrm{}}^{\mathrm{}}𝑑E|A_{00}(E)|^2,$$
(1)
where $`A_{00}(E)`$ is the intraband decay amplitude and $`\mathrm{\Gamma }_S`$ is the electromagnetic decay width of superdeformed state $`|0`$. The energy average of Eq. (1) may be written as the incoherent sum

$$\overline{I_{\mathrm{in}}}=I_{\mathrm{in}}^{\mathrm{av}}+\overline{I_{\mathrm{in}}^{\mathrm{fl}}},$$
(2)
where

$$I_{\mathrm{in}}^{\mathrm{av}}=\overline{I_{\mathrm{in}}^{\mathrm{av}}}=\left(2\pi \mathrm{\Gamma }_S\right)^1_{\mathrm{}}^{\mathrm{}}𝑑E\left|\overline{A_{00}(E)}\right|^2$$
(3)
and

$$\overline{I_{\mathrm{in}}^{\mathrm{fl}}}=\left(2\pi \mathrm{\Gamma }_S\right)^1_{\mathrm{}}^{\mathrm{}}𝑑E\overline{\left|A_{00}^{\mathrm{fl}}(E)\right|^2},$$
(4)
where we have written the decay amplitude as $`A_{00}=\overline{A_{00}}+A_{00}^{\mathrm{fl}}`$ where $`\overline{A_{00}}`$ is a background contribution and $`A_{00}^{\mathrm{fl}}`$ is the fluctuation on that background. In  the background is taken to be

$$\overline{A_{00}}=\frac{\mathrm{\Gamma }_S}{EE_0+i(\mathrm{\Gamma }_S+\mathrm{\Gamma }^{})/2}.$$
(5)
Eq. (5) exhibits the structure of an isolated doorway resonance. The doorway $`|0`$ has an escape width $`\mathrm{\Gamma }_S`$ for decay to the SD state with next lower spin and a spreading width $`\mathrm{\Gamma }^{}`$ for decay to the ND states with the same spin which are reached by tunnelling through the barrier separating the SD and ND wells.

In  it is shown that the auto-correlation function of the decay amplitude is given by

$`\overline{A_{00}^{\mathrm{fl}}(E)A_{00}^{\mathrm{fl}}(E^{})^{}}`$ $``$ $`2\left(2\pi \mathrm{\Gamma }_N/d\right)^1(\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S)^2\overline{A_{00}(E)}^2{\displaystyle \frac{i\mathrm{\Gamma }_N}{EE^{}+i\mathrm{\Gamma }_N}}\overline{A_{00}(E^{})^{}}^2.`$ (6)
When $`E^{}=E`$ this reduces to

$$\overline{\left|A_{00}^{\mathrm{fl}}\right|^2}=2\left(2\pi \mathrm{\Gamma }_N/d\right)^1\frac{\mathrm{\Gamma }_{S}^{}{}_{}{}^{2}\mathrm{\Gamma }_{}^{}{}_{}{}^{2}}{\left[(EE_0)^2+(\mathrm{\Gamma }_S+\mathrm{\Gamma }^{})^2/4\right]^2},$$
(7)
which is the average of the fluctuation contribution to the transition intensity.

The integrals in Eqs. (3) and (4) may be carried out using the calculus of residues. One obtains

$$I_{\mathrm{in}}^{\mathrm{av}}=\frac{1}{1+\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S},$$
(8)
for the average background contribution and

$`\overline{I_{\mathrm{in}}^{\mathrm{fl}}}`$ $`=`$ $`2\left(\pi \mathrm{\Gamma }_N/d\right)^1{\displaystyle \frac{\left(\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S\right)^2}{\left(1+\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S\right)^3}}=2\left(\pi \mathrm{\Gamma }_N/d\right)^1I_{\mathrm{in}}^{\mathrm{av}}\left(1I_{\mathrm{in}}^{\mathrm{av}}\right)^2,`$ (9)
for the average fluctuation contribution to the average decay intensity.

Eq. (9) for $`\overline{I_{\mathrm{in}}^{\mathrm{fl}}}`$ is plotted in Fig. 2 and for comparison we have also plotted a fit formula which was obtained by GW,

$`\overline{I_{\mathrm{in}}^{\mathrm{fl}}}`$ $`=`$ $`\left[10.9139\left(\mathrm{\Gamma }_N/d\right)^{0.2172}\right]\mathrm{exp}\left\{{\displaystyle \frac{\left[0.4343\mathrm{ln}\left(\frac{\mathrm{\Gamma }^{}}{\mathrm{\Gamma }_S}\right)0.45\left(\frac{\mathrm{\Gamma }_N}{d}\right)^{0.1303}\right]^2}{\left(\mathrm{\Gamma }_N/d\right)^{0.1477}}}\right\}.`$ (10)
Qualitative agreement is seen between the two formulae. Our results are strictly valid only when $`\mathrm{\Gamma }_N/d1`$. The dependence of $`\overline{I_{\mathrm{in}}^{\mathrm{fl}}}`$ (and that of $`I_{\mathrm{in}}^{\mathrm{av}}`$) on $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S`$ results from the resonant doorway energy dependence of the decay amplitude $`\overline{A_{00}(E)}`$ \[Eq. (5)\]. This energy dependence also manifests itself in the average of the fluctuation contribution to the transition intensity $`\overline{|A_{00}^{\mathrm{fl}}(E)|^2}`$ \[Eq. (7)\]. GW include precisely the same energy dependence in their calculation by use of an energy dependent transmission coefficient to describe decay to the SD band. This is the reason for our qualitative agreement with GW concerning $`\overline{I_{\mathrm{in}}}`$.

A measure of the dispersion of the calculated $`I_{\mathrm{in}}`$ is given by the variance

$$\overline{\left(\mathrm{\Delta }I_{\mathrm{in}}\right)^2}=\overline{\left(I_{\mathrm{in}}\overline{I_{\mathrm{in}}}\right)^2}.$$
(11)
It is shown in  that

$$\overline{\left(\mathrm{\Delta }I_{\mathrm{in}}\right)^2}=\overline{I_{\mathrm{in}}^{\mathrm{fl}}}^2f_1\left(\xi \right)+2I_{\mathrm{in}}^{\mathrm{av}}\overline{I_{\mathrm{in}}^{\mathrm{fl}}}f_2\left(\xi \right),$$
(12)
where the variable $`\xi `$ is defined by

$`\xi {\displaystyle \frac{\mathrm{\Gamma }_S+\mathrm{\Gamma }^{}}{\mathrm{\Gamma }_N}}={\displaystyle \frac{\mathrm{\Gamma }_S}{\mathrm{\Gamma }_N}}(1+\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S)={\displaystyle \frac{\mathrm{\Gamma }_S}{\mathrm{\Gamma }_N}}I_{\mathrm{in}}^{\mathrm{av}}{}_{}{}^{1}={\displaystyle \frac{\mathrm{\Gamma }^{}}{\mathrm{\Gamma }_N}}(1+\mathrm{\Gamma }_S/\mathrm{\Gamma }^{})^1={\displaystyle \frac{\mathrm{\Gamma }^{}}{\mathrm{\Gamma }_N}}(1I_{\mathrm{in}}^{\mathrm{av}}).`$ (13)
and

$$f_1\left(\xi \right)=\frac{1}{\left(1+\xi \right)}+\frac{\xi }{\left(1+\xi \right)^2}+\frac{\xi ^2}{2\left(1+\xi \right)^3}\text{and}f_2\left(\xi \right)=\frac{1}{2\left(1+\xi \right)}.$$
(14)
Since the variance depends only on $`(\mathrm{\Gamma }_S+\mathrm{\Gamma }^{})/\mathrm{\Gamma }_N`$ in addition to $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S`$ and $`\mathrm{\Gamma }_N/d`$, upon fixing the latter two variables the variance may be considered a function of any one of $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_N`$, $`\mathrm{\Gamma }_S/\mathrm{\Gamma }_N`$, $`\mathrm{\Gamma }^{}/d`$ or $`\mathrm{\Gamma }_S/d`$ \[see Eq. (13)\]. Fig. 2 shows a plot of the standard deviation, $`\sqrt{\overline{\left(\mathrm{\Delta }I_{\mathrm{in}}\right)^2}}`$, \[Eq. (12)\] as a function of $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_N`$ for fixed $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S`$ and $`\mathrm{\Gamma }_N/d`$. Ultimately, the variance like the intensity is a function of the spin of the decaying nucleus and could provide an additional probe to the spin dependence of the barrier separating the SD and ND wells which is contained in the spreading width $`\mathrm{\Gamma }^{}`$ . Our result for the variance of the decay intensity, $`\overline{\left(\mathrm{\Delta }I_{\mathrm{in}}\right)^2}`$ \[Eq. (12)\] has a structure reminiscent of Ericson’s expression for the variance of the cross section . In the case compound nucleus scattering, extraction of the correlation width from a measurement of cross section autocorrelation function permits the determination of the density of states of the compound nucleus . In the present case the variance supplies a second “equation” besides that for $`\overline{I_{\mathrm{in}}}`$. Both equations are functions of $`\mathrm{\Gamma }^{}`$ and $`d`$, since the electromagnetic widths are measured. Thus both $`\mathrm{\Gamma }^{}`$ and $`d`$ can be unambiguously determined.

## 3 Conclusions

In conclusion, we have presented analytic formulae for the energy average and variance of the intraband decay intensity of a superdeformed band. These formulae were derived by making assumptions and approximations which are strictly valid only in the strongly overlapping resonance region, $`\mathrm{\Gamma }_N/d1`$. However, these formulae work well when $`\mathrm{\Gamma }_N/d`$=1 and provide a qualitative description even when $`\mathrm{\Gamma }_N/d`$=0.1. We have revealed that the variance of the decay intensity depends on the correlation length $`\mathrm{\Gamma }_N/(\mathrm{\Gamma }_S+\mathrm{\Gamma }^{})`$ in addition to the two dimensionless variables $`\mathrm{\Gamma }^{}/\mathrm{\Gamma }_S`$ and $`\mathrm{\Gamma }_N/d`$ on which the average of the decay intensity depends.


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# Isospin Symmetry Breaking Effects on the Properties of Asymmetrical Nuclear Matter and 𝛽-Stable Matter

## 1 Introduction

In the calculation of the properties of nucleonic matter, the nucleon-nucleon potential has a crucial role. Recent models of two-nucleon potentials which fit the nucleon-nucleon scattering data with high precision, contain terms which break the isospin symmetry (Stoks et al., 1994; Machleidt and Slaus, 2001; Li and Machleidt, 1998). Isospin symmetry is the invariance under any rotation in the isospin space. But, due to the mass difference between neutral pion and charged pion ($`\mathrm{\Delta }m4.6MeV`$), this symmetry is broken (Stoks et al., 1994; Machleidt and Slaus, 2001; Li and Machleidt, 1998). This means that for the new two-nucleon potentials, the neutral pion exchange is distinguished from charged pion exchange. This distiction implies that the neutron-neutron (nn), neutron-proton (np) and proton-proton (pp) interactions are different and therefore, these potentials are called isospin symmetry breaking (ISB) potentials (Stoks et al., 1994).

Due to the distinction between the neutral pion and charged pion exchange, for the potentials which describe the long range part of the nucleon-nucleon interaction in terms of the one-pion exchange model, the one-pion exchange term is one of the origins of ISB (Stoks et al., 1994; Machleidt and Slaus, 2001; Li and Machleidt, 1998). For the ISB potentials, in the isospin $`T=1`$ states, the distinction between the nn, np and pp potentials is necessary (Stoks et al., 1994). Therefore, in the calculations with these potentials, the difference between the nn, np and pp wave functions should be considered. In our calculations, we use the Reid-93 potential (Stoks et al., 1994). This potential describes the longe range part of the nucleon-nucleon interaction in terms of the one-pion exchange model accounting for the mass difference between the neutral pion $`\pi ^0`$ and charged pions $`\pi ^+`$ and $`\pi ^{}`$. In the Reid-93 potential, for the non-one-pion exchange parts, additional ISB terms have been included in the $`{}_{}{}^{1}S_{0}^{}`$ state potential (Stoks et al., 1994).

In this work, we intent to calculate the various properties of asymmetrical nuclear matter and $`\beta `$-stable matter in two different cases with isospin symmetry (IS) and with isospin symmetry breaking (ISB). By comparing the results of the IS and ISB cases, we study the influence of ISB of nucleon-nucleon interaction on these properties. For the ISB case, we use the Reid-93 potential (Stoks et al., 1994) in which the one-pion exchange potentials for the np and pp (nn) interactions as well as the np and pp (nn) $`{}_{}{}^{1}S_{0}^{}`$ potentials are different. However, for the IS case, we replace the one-pion exchange and $`{}_{}{}^{1}S_{0}^{}`$ potentials of nn and pp interactions with the corresponding np interaction (Stoks et al., 1994). In our calculations, we employ the formalism used in our previous works (Bordbar and Modarres, 1997, 1998; Modarres and Bordbar, 1998; Bordbar and Riazi, 2001, 2002; Bordbar, 2002a,b) in which we consider the distiction between the partial waves with $`M_T=+1`$, $`0`$ and $`1`$. This method is a variational approach based on the cluster expansion of the energy functional containing the state dependent correlation functions. The convergence of the results of this approach has been also tested by calculating the three-body cluster term (Bordbar and Modarres, 1997).

## 2 Isospin Symmetry Breaking Effects on the Asymmetrical Nuclear Matter Properties

The asymmetrical nuclear matter properties are important for studying the supernova collapse and heavy-ion reaction (Lattimer and Prakash, 2000; Li et al., 1997). For asymmetrical nuclear matter, we define the asymmetry parameter $`\beta `$ as

$$\beta =\frac{\rho _n\rho _p}{\rho },$$
(1)
where $`\rho _n`$ and $`\rho _p`$ are the number densities of neutrons and protons respectively, and $`\rho =\rho _n+\rho _p`$ is the total number density. This implies that for symmetrical nuclear matter ($`\rho _n=\rho _p`$) $`\beta =0.0`$ and for the pure neutron matter $`\beta =1.0`$.

In this section, we present our results for the various properties of asymmetrical nuclear matter and then we investigate the effects of ISB on these properties.

The total energy of asymmetrical nuclear matter as a function of total number density for various asymmetry parametrs is given in Figure 1. It is seen that for both IS and ISB cases as the asymmetry parameter increases, the saturation point shifts to the lower densities. However, for the large values of $`\beta `$, the energy curve does not shows any minimum. The changes of total energy due to the inclusion of ISB for nucleon-nucleon interaction are shown in Figure 2. This figure shows that the differences between our results in the ISB and IS cases increase by increasing both density and asymmetry parameter. In Table 1, our results for the differences between the ISB and IS energies at $`\beta =0.0`$ are compared with those of MPM (Muther et al., 1999). It can be seen that our results are in a good agreement with the results of MPM for the Nijm-II potential.

The $`\beta `$-dependence of the total energy of asymmetrical nuclear matter in the ISB case is shown in Figure 3 for different values of density. It can be seen that even in the presence of ISB, the asymmetrical nuclear matter energy is nearly linear in $`\beta ^2`$ and therefore, the higher orders effects of the asymmetry are very small. This confirms the validity of the empirical parabolic law.

In Figure 4, we have shown the effects of ISB on the potential energy of asymmetrical nuclear matter. It is seen that the potential energy difference between the IS and ISB cases increases by increasing asymmetry parameter $`\beta `$. This is due to the fact that by increasing $`\beta `$, the energy contribution of nn interaction increases. Therefore, the difference between the case in which we distinguish between the nn and np interactions (ISB case) and the case in which we replace the nn interaction by the corresponding np interaction (IS case) increases by increasing $`\beta `$. It is also seen that for each value of density and asymmetry parameter, the potential energy shift due to the ISB is positive. This behaviour is reflecting the fact that in the partial wave with isospin $`T=1`$, the $`M_T=0`$ potential is more attractive than the corresponding $`M_T=+1`$ and $`M_T=1`$ potentials (Bordbar, 2003).

The influence of ISB on the saturation point properties of asymmetrical nuclear matter is shown in Table 2. We see that the ISB effects on the saturation density, energy and incompressibility of asymmetrical nuclear matter are generally small, but they are considerable for large $`\beta `$.

The nuclear matter asymmetry energy is of particular interest in astrophysics, especially for studying the supernova mechanism (Lattimer and Prakash, 2000). The asymmetry energy can be approximated as the difference between binding energies of pure neutron matter ($`\beta =1.0`$) and symmetrical nuclear matter ($`\beta =0.0`$). The validity of using this approximation (called parabolic approximation) in calculating the asymmetry energy was shown in Figure 3. Our results for the asymmetry energy calculated for both IS and ISB cases are presented in Figure 5. It can be seen that the changes of asymmetry energy due to the inclusion of ISB increase by inceasing density.

## 3 Isospin Symmetry Breaking Effects on the $`\beta `$-Stable Matter Properties

The properties of $`\beta `$-stable matter are of special importance in astrophysics. The equation of state of $`\beta `$-stable matter is very important for investigating the neutron stars, particularly in their stability (Akmal et al., 1998; Heiselberg and Pandharipande, 2000). The $`\beta `$-stable matter is a composition of nucleons and leptons which is electrically neutral and in $`\beta `$-equilibrium. The $`\beta `$-equilibrium means that there is a balance between the competing processes of electron capture $`e+pn+\nu `$ and $`\beta `$-decay $`ne+p+\overline{\nu }`$. This equilibrium conditions determine the proton fraction ($`x=\rho _p/\rho `$) in $`\beta `$-stable matter. The proton fraction is important for studing the cooling of a neutron star (Prakash, 1994).

In Figure 6, we have plotted our results for the total energy of $`\beta `$-stable matter versus density in the IS and ISB cases. It is seen that by considering ISB for the nucleon-nucleon interaction, the change of $`\beta `$-stable matter energy is small. For example, at density $`\rho =1.0fm^3`$, the energy correction due to the ISB effects is about $`1.6\%`$. Therefore, the effects of ISB on the total energy of $`\beta `$-stable matter are negligible.

The calculated energy contribution of leptons and proton fraction in $`\beta `$-stable matter are shown in Figures 7 and 8. It is found that these properties of $`\beta `$-stable matter are varied by the inclusion of ISB of nucleon-nucleon interaction. This shows that the ISB of nucleon-nucleon interaction affects the conditions of $`\beta `$-equilibrium.

The equation of state of $`\beta `$-stable matter calculated for both IS and ISB cases are shown in Figure 9. It can be seen that the influences of ISB on the equation of state of $`\beta `$-stable matter are ignorable.

## 4 Summary and Conclusion

The two-nucleon potential has a crucial role in the nuclear many-body calculations. By comparing the results of two different cases of isospin symmetry (IS) and isospin symmetry breaking (ISB) for the nucleon-nucleon interaction, we have evaluated the effects of ISB on the different properties of asymmetrical nuclear matter and $`\beta `$-stable matter. It was seen that the changes of total energy, potential energy and asymmetry energy of asymmetrical nuclear matter due to the inclusion of ISB for the nucleon-nucleon interaction increase by increasing both density and asymmetry parameter. It was shown that the empirical parabolic law is valid, even by considering ISB for the nucleon-nucleon interaction. It was indicated that our results for the total energy and the equation of state of $`\beta `$-stable matter in the IS and ISB cases are nearly identical. For $`\beta `$-stable matter, it was shown that the ISB affects the energy contribution of leptons and proton fraction.

## 5 Acknowledgment

Financial support from Shiraz University research council and IPM is gratefully acknowledged.


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# On the nature of ferromagnetism in Ga1-xMnxAs semiconductors

(Version 02.00 – March 16, 2024)

## Abstract

We have performed ab initio calculations within the density-functional theory for Ga1-xMnxAs diluted semiconductors. Total energy results unambiguously show that a quasi-localized $``$ hole, with strong $`p`$-like character, surrounds the fully polarized Mn $``$ $`d^5`$-electrons. Calculations indicate that the holes form an essentially dispersionless impurity band, thus rendering effective-mass descriptions of hole states open to challenge. We obtain estimates both for the $`s=1/2`$ hole and $`S=5/2`$ Mn exchange coupling, and for the distance dependence of the effective Mn-Mn exchange interaction. Results demonstrate that the effective Mn-Mn coupling is always ferromagnetic, thus non-RKKY, and intermediated by the antiferromagnetic coupling of each Mn spin to the holes.

In the last few years, a considerable amount of work has been devoted to the study of diluted magnetic semiconductors (DMS), since the possibility of manipulating both the charge and spin degrees of freedom of carriers in magnetic materials will change qualitatively the efficiency of spintronics devices. The discovery of hole-induced ferromagnetism in p-type (In,Mn)As systems Ohno92  was followed by the successful growth of ferromagnetic (Ga,Mn)As alloys Ohno96 . A quantitative understanding of the physics in these materials is therefore crucial, since ferromagnetic III-V alloys may be readily combined into semiconductor heterostruture systems, opening up a range of applications of optoelectronic devices through the combination of quantum and magnetic phenomena in these materials. However, in order to develop full-scale applications, one needs to elucidate several issues in relation to these systems. In the case of Ga1-xMnxAs semiconductors, it is well known that Mn forms acceptors when in substitutional Ga lattice sites (MnGa). One of the standing issues is related to the fact that the critical temperature and hole concentration, as a function of Mn composition in Ga1-xMnxAs, are crucially dependent on the details of growth conditions vanEsch97 ; Matsukura98 ; Ohno99a ; Potashnik01 ; Edmonds02 ; Seong02 ; Asklund02 ; Yu02a ; Yu02b ; Potashnik02 ; Moriya03 ; dosSantos , even in as-grown samples; note, in particular, that for $`x5\%`$, $`T_c`$ ranges from $`30`$ K to 110 K, with the highest temperature Matsukura98  of 110 K only being reproduced by other groups after post-growth annealing Potashnik01 ; Potashnik02 ; Hayashi01 . The measured hole concentration $`p`$ as a function of $`x`$ similarly reveals discrepancies both in trends and in order of magnitude; note that different experimental techniques (Hall resistance Potashnik01  and Raman scattering Seong02 ) applied to the same $`x=0.083`$ sample yield values of $`p`$ differing by as much as a factor of 10.

From the theoretical point of view, different models have been proposed to describe the electronic and magnetic properties of (Ga,Mn)As. The generally accepted view is that a given Mn ion interacts with the holes via a local antiferromagnetic Kondo-like exchange coupling $`J_{hd}N\beta (a^3/4)`$ ($`a`$ is the GaAs lattice parameter) between their magnetic moments Ohno99a ; Dietl97 ; Ohno01 ; this interaction is thought to lead to a polarization of the hole subsystem, which would then give rise to an effective ferromagnetic coupling between the Mn moments. Early attempts treated the holes within an $`sp`$ parabolic-band effective-mass approximation; this approach is in conflict with recent photoemission studies Asklund02  and infrared measurements Singley02 , which indicate that the holes form a relatively flat impurity band at the Fermi energy, instead of residing in an unaltered GaAs valence band. In particular, infrared spectroscopic measurements estimated the hole effective mass within the range $`0.7m_e<m^{}<15m_e`$ for an $`x=0.52`$ sample, and even larger values at higher dopings Singley02 . As a consequence, any treatment of holes within an effective-mass approximation, including attempts in the direction of incorporating aspects such as a Kohn-Luttinger treatment of the valence states Dietl01b ; Abolfath01 , are quite clearly open to question. The same applies to estimates of $`N\beta 1.53`$ eV Matsukura98 ; Ohno01 , which are obtained from resistivity fits to experimental data resorting to a hole effective mass $`m^{}=0.5m_e`$.

Therefore, it is fundamental to have a highly accurate microscopic description of the electronic and magnetic properties of Ga1-xMnxAs DMS. Here we perform a detailed ab initio study of the physical origin of the observed Mn-Mn ferromagnetic coupling. Our total energy results provide unambiguous evidence that (i) the impurity states are essentially localized and hence almost dispersionless, thus rendering any effective-mass picture inapplicable, and (ii) the effective coupling is always ferromagnetic (thus non-RKKY), intermediated by an antiferromagnetic coupling of each Mn spin to the holes. In addition, we have also provided reliable values for the Mn-hole exchange coupling, as well as for the anisotropy- and direction-dependence of the effective (i.e., if the hole degrees of freedom were integrated out) coupling between Mn spins.

We have performed total energy calculations based on the density-functional theory (DFT) within the generalized-gradient approximation (GGA) for the exchange-correlation potential, with the electron-ion interactions described using ultrasoft pseudopotentials Vanderbilt90 . A plane wave expansion up to 230 eV as implemented in the VASP code Kresse93  was used, together with a 128-atom and a 250- atom fcc supercell and the $`L`$-points for the Brillouin zone sampling. The positions of all atoms in the supercell were relaxed until all the forces components were smaller than 0.02 eV/Å. We have also checked for spin-orbit effects through the projector augmented-wave (PAW) method Kresse99  and found that they may be safely neglected.

Let us first consider the case of a single isolated MnGa acceptor. From total energy calculations for neutral (MnGa)0 and negatively charged (MnGa)- defects, with a 250-atom supercell, we obtain a localized acceptor level lying at 0.1 eV above the top of the valence band, in good agreement with the 0.11 eV experimental value Mnlevel . Moreover, the ground state of the MnGa defect is consistent with the picture of a $``$ hole interacting antiferromagnetically with the $``$ $`\mathrm{S}=5/2`$ spin of the $`d^5`$-configuration at the Mn site. The robustness of this state is illustrated by the fact that the ferromagnetic configuration with an $``$ hole lies $``$ 0.25 eV above the antiferromagnetic one. Figure 1(a) shows the difference $`m(𝐫)\rho _{}(𝐫)\rho _{}(𝐫)`$ for the MnGa defect, where $`\rho _\sigma `$ is the total charge density in the $`\sigma `$-polarized channel. We note that near the MnGa acceptor, the local magnetization has a strong $``$ $`d`$-like character, due essentially to the valence-band resonant $`d^5`$ electrons, whereas as one approaches its As neighbors, the character changes to $``$ p-like. The signature of the above mentioned antiferromagnetic interaction consists of a sign change in $`m(𝐫)`$ as one moves from the Mn site to any of its neighboring As. In order to probe the extent of the electronic charge associated with the MnGa defect, the difference between $`\rho _{}(𝐫)+\rho _{}(𝐫)`$ calculated for the MnGa state and the GaAs host is depicted in Figure 1(b). One clearly notes the localized nature of the defect, as the charge difference is essentially confined within the region surrounding the Mn site.

The origin of ferromagnetism in diluted Ga1-xMnxAs semiconductors may be elucidated by focusing on interacting MnGa substitutional defects in a 128-atom supercell, considering both a ferromagnetic as well as an antiferromagnetic allignment between the Mn spins. We have performed calculations for two Mn substitutional atoms in configurations corresponding to all inequivalent positions within the supercell, i.e., Mn-Mn distances varying from 4.06 Å up to 11.48 Å. Our total energy results yield an unanbiguous Mn-Mn ferromagnetic ground state in all cases so . Figure 2 shows the net magnetization $`m(𝐫)`$ isosurfaces for two Mn defects in nearest-neighbor and next-nearest neighbor positions (for the Ga sublattice), with parallel and anti-parallel Mn spins. In Fig. 2, the Mn atoms are at the center of the spherical-like regions of $`m(𝐫)`$, whereas the $`p`$-like regions are always centered on As atoms. Note that, irrespective of the relative orientation of the Mn-Mn spins, the antiferromagnetic coupling between the Mn and hole spins is always maintained. In the Mn-Mn antiferromagnetic case, this leads to the appearence of nodes in $`m(𝐫)`$, which contributes to increase its energy relative to the ferromagnetic state. Another important feature illustrated in Fig. 2 is the fact that, again, the Mn-Mn defect is essentially localized, although the magnetization density clearly spreads out from one MnGa site to the other. The picture that emerges is that of a cloud of $``$ holes surrounding the substitutional Mn, with the distribution of quasi-localized holes giving rise to a nearly dispersionless impurity band, so that a description via the effective-mass approximation would be inappropriate.

From the difference between total energies of the ferro- and antiferromagnetic configurations of the $`s=1/2`$ hole and the $`S=5/2`$ Mn spins, assuming an interaction of the type $`N\beta 𝐬𝐒`$, and taking into account the contribution due to images in neighboring supercells, one may calculate the strength of the Kondo-like antiferromagnetic exchange coupling $`N\beta +0.1`$ eV. This result contrasts with the previous estimates of $`N\beta 1.53`$ eV Matsukura98 ; Ohno01 . We note that these larger values are open to question, as they are obtained via fittings, to experimental data, of results based on the effective-mass approximation with a hole effective mass $`m^{}=0.5m_e`$. We have also estimated, from total energy calculations, the effective exchange coupling between pairs of $`S=5/2`$ Mn spins, $`J_{MnMn}`$, as a function of the Mn-Mn distance, for all inequivalent pair positions within the supercell (for a Mn-Mn interaction modelled through $`J_{MnMn}𝐒_{Mn_i}𝐒_{Mn_j}`$). In Fig. 3 we display the theoretical predictions for $`J_{MnMn}`$. The results clearly show that the coupling between the Mn spins is always ferromagnetic, irrespective of their relative distance. As it is well known that the bare coupling between two Mn spins should be antiferromagnetic, one concludes that the resulting Mn-Mn ferromagnetic effective coupling, in Ga1-xMnxAs, is essentially intermediated by the antiferromagnetic coupling of each Mn spin to the quasi-localized holes. Also, the observed non-monotonic behavior of $`J_{MnMn}(𝐫)`$ should be attributed to the anisotropic character of the effective interaction, as it may be inferred from Fig. 2. The inescapable conclusion from Fig. 3 is that an RKKY description for the Mn-Mn interaction in Ga1-xMnxAs is ruled out. Here we note that this result contrasts with the RKKY coupling obtained by Zhao et al. Zhao03  in the case of MnxGe1-x.

The data in Fig. 3 can be used to estimate the critical temperature at a given Mn concentration, which, within a simple mean-field theory is given by

$$k_BT_c=\frac{S(S+1)}{3}|J_0|,$$
(1)
with

$$J_0=\underset{𝐫}{}J(𝐫)=\left(\frac{\overline{z_1}}{2}J_1+\frac{\overline{z_2}}{2}J_2+\frac{\overline{z_3}}{2}J_3+\mathrm{}\right),$$
(2)
where $`J_1,J_2,\mathrm{}`$ stand for first-, second-,…, -neighbor interactions, the values of which are given in Fig. 3, and the $`\overline{z_i}`$ are the corresponding configurationally-averaged coordination numbers in the Ga sublattice. If we take $`\overline{z_i}=fz_i`$, with $`f`$ being the fraction of *active* Mn sites, which is roughly $`x/3`$, one obtains $`T_c=4\times 10^3x`$ K, in qualitative agreement with the low-density behavior observed experimentally Matsukura98 .

One should mention that the discrepancies between different experimental data indicate that the magnetic, structural, and electronic properties of as-grown Ga1-xMnxAs alloys are extremely sensitive to the actual molecular-beam epitaxy (MBE) growth conditions, such as, for example, growth temperature and beam flux ratios. In fact, this is to be expected, since the holes provided by the MnGa acceptors may be compensated by defects such as arsenic antisites (AsGa) donors, Mn interstitials (MnI), MnI-MnGa pairs, MnAs complexes, etc. Of course, the situation with respect to annealed Ga1-xMnxAs samples is rather more complicated, and a proper analysis of experimental measurements performed in after-annealing samples must involve a realistic modelling of diffusion processes involving several defects, formation of random precipitates, clustering effects, etc. Therefore, we emphasize that a proper understanding of the physics of Ga1-xMnxAs alloys must involve a microscopic description of the effect of different defects on their electronic and magnetic properties.

In conclusion, we have provided a detailed ab initio study of the physical origin of the Mn-Mn ferromagnetic coupling, by considering isolated MnGa defects, as well as two substitutional Mn per supercell, in various relative positions. Our total energy calculations provide unambiguous evidence that the effective coupling is always ferromagnetic, and thus non-RKKY, and intermediated by an antiferromagnetic coupling of each Mn spin to the quasi-localized holes.

Partial financial support by the Brazilian Agencies CNPq, CENAPAD-Campinas, Rede Nacional de Materiais Nanoestruturados/CNPq, FAPESP, FAPERJ, and Millenium Institute for Nanosciences/MCT is gratefully acknowledged.


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# Electronic structures of Zn1-xCoxO using photoemission and x-ray absorption spectroscopy

## Abstract

Electronic structures of Zn1-xCoxO have been investigated using photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). The Co $`3d`$ states are found to lie near the top of the O $`2p`$ valence band, with a peak around $`3`$ eV binding energy. The Co $`2p`$ XAS spectrum provides evidence that the Co ions in Zn1-xCoxO are in the divalent Co2+ ($`d^7`$) states under the tetrahedral symmetry. Our finding indicates that the properly substituted Co ions for Zn sites will not produce the diluted ferromagnetic semiconductor property.

Diluted magnetic semiconductors (DMSs) are considered as good candidates for spintronics materials because of the possibility of incorporating the spin degree of freedom in traditional semiconductors Furd88 ; Wolf01 . Motivated by the recent theoretical calculations by Dietl et al. Dietl00  which predicted room-temperature ferromagnetism in Mn-doped ZnO, Zn1-xTxO systems (T$`=3d`$ transition-metal atom) have been investigated extensively. Indeed there were reports that Zn1-xMnxO epitaxial thin films exhibited ferromagnetic properties Fuku99 ; Jung02  and that Zn1-xCoxO films showed ferromagnetism with the Curie temperature $`\mathrm{T}_\mathrm{C}300`$ K Ueda01 . However, the reproducibility is somewhat questionable, and there are contradicting reports on Co-doped ZnO Ueda01 ; Kim02 ; Lee02 . Technologically ZnO-based DMSs of Zn1-xTxO attract much attention due to the cheapness and abundance of ZnO, and the easy solubility of T atoms in ZnO up to several ten $`\%`$ Fuku99 ; Jin00 . In addition, since ZnO has a wide band gap energy of $`3.4`$ eV, ZnO-based DMSs would be useful for short wavelength magneto-optical applications.

In order to understand the magnetic interaction in Zn1-xTxO, it is essential to understand the electronic structure of the doped $`3d`$ T impurities in Zn1-xTxO. Photoemission spectroscopy (PES) is one of the powerful experimental methods for providing direct information on the electronic structures of solids. To our knowledge, only a few PES studies have been reported on Zn1-xTxO: the PES study on Zn1-xMnxO Mizo02  and the Co $`2p`$ core-level PES spectra for Zn1-xCoxO Lee02 .

In this study we have investigated the electronic structure of homogeneous bulk samples of Zn1-xCoxO using PES and x-ray absorption spectroscopy (XAS). Differently from previously reported film samplesUeda01 , magnetic properties of our bulk Zn1-xCoxO samples revealed that the Co-Co magnetic interaction is dominated by the antiferromagnetic coupling Yoon03 . Magnetic susceptibility at high temperature exhibits a typical Curie-Weiss behavior with negative $`\mathrm{T}_\mathrm{C}`$ and the magnetization of Co ion is reduced with increasing the Co ion concentration reflecting an increase in average antiferromagnetic interaction between Co ions. Hence the present bulk sample is not a diluted ferromagnetic semiconductor.

Polycrystalline Zn1-xCoxO samples ($`x=0,0.1`$) were synthesized using the standard solid-state reaction method. Zn1-xCoxO samples were obtained by sintering a mixed powder of ($`1x`$)ZnO$`+x`$CoO at T $`1400^{}`$ C for $`2`$ hours followed by the furnace cooling in air. The x-ray diffraction (XRD) analysis showed that all the samples have the single phase of the Wurtzite structure with no impurity phase. Valence-band PES, XAS and Co $`2p3d`$ resonant photoemission spectroscopy (RPES) measurements were performed at the 2B1 and 8A1 beamlines of the PAL. Samples were cleaned in situ by repeated scraping with a diamond file and the data were obtained at room temperature with the pressure better than $`4\times 10^{10}`$ Torr. The Fermi level $`\mathrm{E}_\mathrm{F}`$ calib  and the overall instrumental resolution (FWHM) of the system were determined from the valence-band spectrum of a sputtered Au foil in electrical contact with a sample. The FWHM was about $`0.10.6`$ eV between a photon energy $`h\nu 30`$ eV and $`h\nu 600`$ eV. All the spectra were normalized to the mesh current. The XAS spectra were obtained by employing the total electron yield method. The experimental energy resolution for the XAS data was set to $`0.2`$ eV at the Co $`2p`$ absorption threshold ($`h\nu `$ 700 eV). Core-level spectra and the valence-band spectrum with $`h\nu =1486.6`$ eV were obtained by using the monochromatized Al $`K\alpha `$ radiation with a FWHM of $`0.6`$ eV.

We have measured the valence-band PES spectra of Zn1-xCoxO ($`x=0,0.1`$) over a wide several photon energy range 25 eV $`h\nu `$ 1486.6 eV, which includes the Co $`2p3d`$ RPES energies (see Fig. 2). Our valence-band PES spectrum of ZnO agrees with the existing data in the literature Ruckh94 . Valence-band spectra for ZnO and Zn0.9Co0.1O were rather similar, showing two large structures, one sharp peak around 11 eV binding energy (BE), and the other broad band between $`3`$ eV and $`7`$ eV BE. The former and latter peaks are assigned as the Zn $`3d`$ and O $`2p`$ emissions, respectively. They also reveal negligible emission near $`\mathrm{E}_\mathrm{F}`$, reflecting that both ZnO and Zn0.9Co0.1O are insulating.

The left panel of Fig. 1 compares the on-resonance ($`h\nu 777.1`$ eV) and off-resonance ($`h\nu 776.4`$ eV) spectra for Zn0.9Co0.1O in the Co $`2p_{3/2}3d`$ RPES, which are scaled to each other at $`7`$ eV BE. The difference between on-resonance and off-resonance can be considered as representing the Co $`3d`$ partial spectral weight distribution (PSW) Kang02 . The right panel of Fig. 1 compares the valence-band spectrum of Zn0.9Co0.1O to that of ZnO, obtained with $`h\nu =1486.6`$ eV. The differences between $`x=0`$ and $`x=0.1`$ also reflect the effect of the Co $`3d`$ states. In both cases the differences are shown at the bottom, which are very similar to each other, showing a peak around $`3`$ eV BE and negligible emission near $`\mathrm{E}_\mathrm{F}`$ scale . These results provide evidence that the Co $`3d`$ states in Zn1-xCoxO are located near the top of the O $`2p`$ valence band.

The extracted Co $`3d`$ PSW reveals almost no emission between $`\mathrm{E}_\mathrm{F}`$ and 2 eV BE. This feature does not agree with the calculated Co $`3d`$ PDOS (partial density of states), obtained from the LSDA (local spin-density approximation) band structure calculation Sato02 . The calculated Co $`3d`$ PDOS for Zn0.75Co0.25O shows a sharp $`e_g^2`$ peak near $`\mathrm{E}_\mathrm{F}`$. To resolve this discrepancy, more elaborate calculations such as LSDA$`+U`$ incorporating the Coulomb correlation $`U`$ between Co $`3d`$ electrons will be required because it is well known that the LSDA calculation does not properly describe the electronic structures of insulators with strongly correlated electrons Park00 .

Figure 2 compares the Co $`2p`$ XAS spectrum of Zn0.9Co0.1O with those of reference Co oxides, having the formal Co valences of $`2+`$ (CoO, Ref. Regan01 ) and $`3+`$ (LiCoO2, Ref. Elp91 ), and that of Co metal (Ref. Regan01 ). Note that Co ions both in CoO and LiCoO2 are located at the octahedron ($`O_h`$) centers. The peak positions and the line shape of the T $`2p`$ XAS spectrum depend on the local electronic structure of the T ion, providing the information about the valence state and the ground state symmetry of the T ion Groot90 ; Laan92 ; Kim03 . The Co $`2p_{3/2}`$ and $`2p_{1/2}`$ spectral parts are clearly separated by the large $`2p`$ core-hole spin-orbit interaction, and the core-hole lifetime broadening is small, resulting in the sharp multiplet structures. The Co $`2p`$ XAS spectrum of Zn0.9Co0.1O looks similar to that of CoO except for the absence of the low-$`h\nu `$ shoulder ($`h\nu 776`$ eV), but quite different from those of LiCoO2 and Co metal. This observation indicates that Co ions in Zn1-xCoxO might be in the divalent Co2+ valence states, but not in the trivalent Co3+ valence states, and that the formation of the Co metal cluster in our Zn1-xCoxO samples can be ruled out.

In order to estimate the valence state of Co ions in the ground states, we have analyzed the Co $`2p`$ XAS spectrum of Zn0.9Co0.1O within the cluster model where the effects of the multiplet interaction, the crystal field, and the hybridization with the O $`p`$ ligands are included Laan92 . The calculated XAS spectrum is shown at the bottom of Fig. 2. We have found that including only one configuration, corresponding to Co2+ ($`d^7`$), and the tetrahedral ($`T_d`$) crystal field energy of $`10Dq=0.6`$ eV yields a good fit for the measured $`2p`$ XAS spectrum cluster . The analysis shows that it is not necessary to include the charge-transfer configuration, $`d^{n+1}\underset{¯}{L}^1`$ ($`\underset{¯}{L}`$: a ligand hole), indicating that the hybridization between Co $`3d`$ and O $`p`$ orbitals is small, in contrast to Mn-doped ZnO case Mizo02 . We have checked that small changes in the parameters do not affect the overall spectral shape including the prominent peak positions. Based on the calculated XAS spectrum, one can conclude that the doped-Co ions in Zn1-xCoxO are divalent in the ground states, i.e., Co2+ ($`S=3`$) under the $`T_d`$ symmetry with a small crystal field energy LS . Our finding suggests that, in our samples, Co ions substitute properly for the Zn sites with Co2+ valence states. In view of no long range ferromagnetic order in our samples, the reported DMS properties in some Co-doped ZnO Ueda01 ; Lee02  are likely to be extrinsic, that is, to originate from Co cluster or other impurity phases.

In conclusion, the electronic structures of bulk Zn1-xCoxO samples have been investigated by employing PES and XAS. According to the Co $`2p3d`$ RPES and the careful comparison between $`x=0`$ and $`x=0.1`$, the Co $`3d`$ states in Zn1-xCoxO are found to lie near the top of the O $`2p`$ valence band with a peak around $`3`$ eV BE. The measured Co $`2p`$ XAS spectrum shows that the ground states of Co ions in Zn1-xCoxO are the divalent Co2+ states under the $`T_d`$ symmetry corresponding to the total spin of $`S=3`$ per Co ion. Our finding suggests that the properly substituted Co ions in Co-doped ZnO do not produce the DMS property with the long range ferromagnetic order.

Acknowledgments$``$ This work was supported by the KRF (KRF-2002-070-C00038) and by the KOSEF through the CSCMR at SNU and the eSSC at POSTECH. The PAL is supported by the MOST and POSCO in Korea.


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# 1 Introduction

## 1 Introduction

In addition to its technological relevance, epitaxial crystal growth is highly attractive from a theoretical point of view. It offers many challenging open questions and provides a workshop in which to develop novel methods for the modeling and simulation of non-equilibrium systems, in general.

In particular, strained heteroepitaxial crystal growth attracts significant interest as a promising technique for the production of, for instance, high quality semiconductor films. Recent overviews of experimental and theoretical investigations can be found in, e.g., . A particular attractive aspect is the possibility to exploit self–organizing phenomena for the fabrication of nanostructured surfaces by means of Molecular Beam Epitaxy (MBE) or similar techniques.

In many cases, adsorbate and substrate materials crystallize in the same lattice but with different bulk lattice constants. Frequently, one observes that the adsorbate grows layer by layer, initially, with the lateral spacing of atoms adapted to the substrate. The misfit induces compressive or tensile strain in this pseudomorphic  film and, eventually, misfit dislocations will appear. These relax the strain and the adsorbate grows with its natural lattice constant far from the substrate, eventually.

Dislocations will clearly dominate strain relaxation in sufficiently thick films and for large misfits. In material combinations with relatively small misfit an alternative effect governs the initial growth of thin films: Instead of growing layer by layer, the adsorbate aggregates in three-dim. structures. The term 3D-islands is commonly used to indicate that these structures are spatially separated. The situation is clearly different from the emergence of mounds due to the Ehrlich-Schwoebel (ES) instability , for instance.

At least two different growth scenarios display 3D-island formation: In Volmer-Weber growth, such structures appear immediately upon the substrate when depositing the mismatched material. The situation resembles the formation of non-wetting droplets of liquid on a surface. It is frequently observed in systems where adsorbate and substrate are fundamentally different, an example being Pb on a graphite substrate .

In the following we concentrate on the so–called Stranski-Krastanov (SK) growth mode, where 3D-islands are found upon a pseudomorphic wetting-layer (WL) of adsorbate material . Two prominent prototype SK–systems are Ge/Si and InAs/GaAs where, as in almost all cases discussed in the literature, the adsorbate is under compression in the WL.

In order to avoid conflicts with more detailed definitions and interpretations of the SK growth mode in the literature we will resort to the term SK-like growth  in the following. It summarizes the following sequence of phenomena during the deposition of a few monolayers (ML) of material:

1. The layer by layer growth of a pseudomorphic adsorbate WL up to a kinetic thickness $`h_{\mathrm{WL}}^{}`$.
2. The sudden appearance of 3D-islands, marking the so-called 2D-3D- or SK-transition
3. Further growth of the 3D-islands, fed by additional deposition and by incorporation of surrounding WL atoms
4. The observation of separated 3D-islands of similar shapes and sizes, on top of a WL with reduced stationary thickness $`h_{\mathrm{WL}}`$.

Besides these basic processes a variety of phenomena can play important roles in the SK-scenario, including the interdiffusion of materials and the segregation of compound adsorbates. These effects are certainly highly relevant in many cases, see  and other contributions to this volume . However, SK–like growth is observed in a variety of material systems which may or may not display these specific features. For instance, intermixing or segregation should be irrelevant in the somewhat exotic case of large organic molecules like PTCDA deposited on a metal substrate, e.g. Ag(111). Nevertheless, this system displays SK–like growth in excellent accordance with the above operative definition .

Despite the extensive investigation of SK–growth, a complete detailed theoretical picture is still lacking, apparently. This concerns in particular the nature of the 2D-3D transition. One problem clearly lies in the richness of the phenomenon. On the other hand, the very diversity of SK–like systems gives rise to the hope that this growth scenario might be governed by a few basic universal mechanisms. Accordingly, it should be possible to capture and identify these essential features in relatively simple prototype systems.

This hope motivates the investigation of simplifying models without aiming at the reproduction of material specific details. Some of the key questions in this context are: under which conditions does a WL emerge and persist? How does its thickness before and after the SK-transition depend on the growth conditions? Which microscopic processes trigger and control the sudden formation of 3D-islands? How do the island size and their spatial arrangement depend on the parameters of the system?

Following earlier investigations of related phenomena, e.g. , we choose a classical pair potential ansatz to represent the interactions between atoms in our model. Here, we restrict our studies to the fairly simple case of a modified Lennard-Jones (LJ) system in $`1+1`$ spatial dimensions, i.e. growth on a one-dim. substrate surface. As we interprete our model as a cross-section of the physical $`(2+1)`$-dim. case, we still use the common term 2D-3D transition for the formation of multilayer from monolayer islands.

We investigate our model by means of Kinetic Monte Carlo (KMC) simulation, see e.g.  for an introduction and overview. This concept has proven useful in the study of non-equilibrium dynamical systems in general and in particular in the context of epitaxial growth, see e.g. .

Most frequently, pre-defined lattices are used for the representation of the crystal. So-called Solid-On-Solid (SOS) models which neglect lattice defects, bulk vacancies, or dislocations have been very successful in the investigation of various relevant phenomena, including scenarios of kinetic roughening or mound formation due to instabilities . There is, however, no obvious way of including mismatch and strain effects in a lattice gas model. A potential route is to introduce additional elastic interactions between neighboring atoms in an effective fashion. In fact, such models of hetero-systems have been studied in some of the earliest Kinetic Monte Carlo simulations of epitaxial growth , see  for a recent example of a so-called ball and spring model. In alternative approaches the strain field of a given configuration is evaluated using elasticity theory as, for instance, in .

In order to account for strain effects more faithfully, including potential deviations from a perfect lattice structure, it is essential to allow for continuous particle positions. Given at least an approximation for the interatomic potentials, a Molecular Dynamics (MD) type of simulation  would be clearly most realistic and desirable, see  for one example in the context of heteroepitaxial growth. However, this method suffers generally from the restriction to short physical times on the order of $`10^6s`$ or less. MBE relevant time scales of seconds or minutes do not seem feasible currently even when applying sophisticated acceleration techniques .

Here, we put forward an off-lattice KMC method which has been introduced in  and apply it in the context of the SK-scenario. Some of the results have been published previously in less detail . The paper is organized as follows: in the next section we outline the model and simulation method. Before analysing the actual SK-like growth in section 4 we present some basic results concerning various diffusion scenarios in section 3. In the last section we summarize and discuss open questions and potential extensions of our work.

## 2 Model and method

In our off-lattice model we consider pairwise interactions given by LJ-potentials of the form

$$U_{ij}(U_o,\sigma )=\mathrm{\hspace{0.17em}4}U_o\left[\left(\frac{\sigma }{r_{ij}}\right)^{12}\left(\frac{\sigma }{r_{ij}}\right)^6\right],$$
(1)
where the relative distance $`r_{ij}`$ of particles $`i`$ and $`j`$ can vary continuously. As a widely used approximation we cut off interactions for $`r_{ij}>3\sigma `$.

The choice of the parameters $`\{U_o,\sigma \}`$ in Eq. (1) characterizes the different material properties in our model: interactions between two substrate (adsorbate) particles are specified by the sets $`\left\{U_s,\sigma _s1\right\}`$ and $`\{U_a,\sigma _a\}`$, respectively. Instead of a third independent set we set $`U_{as}=\sqrt{U_sU_a},\sigma _{as}=\left(\sigma _s+\sigma _a\right)/2`$ for the inter-species interaction.

As the lattice constant of a monoatomic LJ crystal is proportional to $`\sigma `$, the relative misfit is given by $`ϵ=\left(\sigma _a\sigma _s\right)/\sigma _s`$. Here we consider only cases with $`\sigma _a>\sigma _s`$, i.e. positive misfits $`ϵ`$ on the order of a few percent. For the simulation of SK-like growth we set $`U_s>U_{as}>U_a`$. In such systems, the formation of a WL and potential layer by layer growth should be favorable, in principle. If not otherwise specified, we have set the misfit to $`ϵ=4\%`$, a typical value for SK-systems, and used the LJ-prefactors $`U_s=1.0eV,U_a=0.74eV,U_{as}0.86eV`$.

Growth takes place on a substrate represented by six atomic layers, with the bottom layer fixed and periodic horizontal boundary conditions. In the following we mostly refer to systems with $`L=800`$ particles per substrate layer, additional simulations with $`L=400`$ or $`600`$ revealed no significant $`L`$-dependence of the results presented here.

The deposition of single adsorbate particles is performed with a rate $`R_d=LF`$, where $`F`$ is the deposition flux. As we interprete the substrate lattice constant as our unit of length, flux and deposition rate (measured in ML$`/s`$) assume the same numerical values.

The rates of all other significant changes of the configuration are given by Arrhenius laws. We consider only hopping diffusion events at the surface and neglect bulk diffusion, exchange processes or other concerted moves. Furthermore, diffusion is restricted to adsorbate particles at the surface whereas jumps of substrate particles onto the surface are not considered. As we will demonstrate in a forthcoming publication, these simplifications are justified for small misfits $`ϵ`$ in the LJ-system because the corresponding rates are extremely low, see also .

The rate $`R_i`$ for a particular event $`i`$ is taken to be of the form

$$R_i=\nu _o\mathrm{exp}\left[\frac{E_i}{k_BT}\right]$$
(2)
where $`T`$ is the simulation temperature and $`k_B`$ the Boltzmann constant. For simplicity, we assume that the attempt frequency $`\nu _o`$ is the same for all diffusion events. In order to relate to physical units we use $`\nu _o=10^{12}s^1`$ wherever numerical results are given. The activation barriers $`E_i`$ are calculated on–line given the actual configuration of the system. This can be done by a minimal energy path saddle point calculation . Here, we use a frozen crystal  approximation which speeds up the calculation of barriers significantly, see  for an application in the context of strained surfaces. Note that the calculations are particularly simple in 1+1 dimensions: the path between neighboring local minima of the potential energy is uniquely determined and the transition state corresponds to the separating local maximum.

An important modification concerns interlayer diffusion. LJ-systems in 1+1 dimensions display a strong additional barrier which hinders such moves at terrace edges . This so–called Ehrlich-Schwoebel (ES) effect is by far less pronounced in (2+1)-dim. systems, because interlayer moves follow a path through an energy saddle point rather than the pronounced maximum at the island edge. In our investigation of the SK-like scenario we remove the ES-barrier for all interlayer diffusion events by hand. One motivation is the above mentioned over-estimation in one dimension. More importantly, we wish to investigate strain induced island formation without interference of the ES instability. Note that the latter leads to the formation of mounds even in homoepitaxy .

The rates for deposition and diffusion are used in a rejection-free KMC simulation . Using a binary search tree technique, one of the possible events $`j`$ is drawn with probability $`R_j/R`$, where $`R=(R_d+_iR_i)`$ is the total rate of all potential changes. Time is advanced by a random interval $`\tau `$ according to the Poisson distribution $`P(\tau )=Re^{R\tau }`$ .

In order to avoid the artificial accumulation of strain due to inaccuracies of the method, the potential energy should be taken to the nearest local minimum by variation of all particle positions in the system. This relaxation process affects both, adsorbate and substrate atoms. In order to reduce the computational effort, we restrict the variation to particles within a radius $`3\sigma _s`$ around the location of the latest event, in general. The global minimization procedure is performed only after a distinct number of steps. It is important to note, that both procedures do not lead to a substantial rearrangement. Significant changes of the activation energies due to relaxation signal the necessity to perform the global procedure more frequently.

## 3 Diffusion processes

Before analysing the SK-like scenario, we compare the barriers for hopping diffusion in various settings on the surface. The investigation of systems like Ge/Si(001) reveal a very complicated scenario due to anisotropies and the influence of surface reconstructions . For Ge on Ge(111) the barrier for hopping diffusion is higher on the surface of a compressed crystal, whereas diffusion is faster on relaxed Ge .

LJ- or similar models do not reproduce this feature, in general. Schroeder and Wolf  consider (2+1)-dim. single species LJ-systems and evaluate the diffusion barrier for a single adatom on surfaces in various lattice types. Among other results they find that mechanical compression of the crystal lowers the barrier for surface diffusion. However, in the mismatched two species system, it is more important to compare diffusion on (a) the substrate, (b) the WL and (c) the surface of partially relaxed islands.

The strong adsorbate-substrate interaction $`(U_{as}>U_a)`$ favors the formation of a WL, but it also yields deep energy minima and a relatively high diffusion barrier for adsorbate particles on the substrate. This effect is much weaker for particles on a complete wetting monolayer of adsorbate and, hence, the corresponding diffusion barrier is significantly lower. The faster diffusion further stabilizes the WL, as deposited particles will reach and fill in gaps easily. In principle, the trend extends to the following layers. However, due to the short range nature of the LJ-potential the influence of the substrate essentially vanishes on WL of three or more monolayers. With the example choice $`ϵ=4\%`$ and $`U_s=1.0eV,U_a=0.74eV,U_{as}0.86eV`$ we find an activation barrier of $`E_a^00.57eV`$ for adsorbate diffusion on the substrate and $`E_a^1E_a^20.47eV`$ for diffusion on the first and second adsorbate layer, respectively.

For the SK-scenario the diffusion on islands of finite extension is particularly relevant. Figure 1 shows the barriers for diffusion hops on islands of various heights located upon a wetting monolayer. We wish to point at two important features: (1) Diffusion on top of islands is, in general, slower than on the WL and the difference increases with the island height. In our model, this is an effect of the partial relaxation or over-relaxation in the island top layer. (2) Depending on the lateral island size and its height, there is a more or less pronounced diffusion bias towards the island center, reflecting the spatially inhomogeneous relaxation. A similar effect has been observed in $`(2+1)`$ dim. LJ-systems .

Note that (2) has to be distinguished from the diffusion bias imposed by the ES-effect, which would be present even in homoepitaxy and with particle positions restricted to a perfect undisturbed lattice.

Clearly, (1) and (2) favor the formation of islands upon islands and hence play an important role in SK-like growth. They concern adatoms which are deposited directly onto the islands as well as particles that hop upward at edges, potentially. As we will argue in the following section, upward diffusion moves play the more important role in the 2D-3D transition of our model.

## 4 SK-like growth scenario

In our investigation we follow a scenario which is frequently studied in experiments : In each simulation run a total of 4 ML adsorbate material is deposited at rates in the range $`0.5ML/sR_d9.0ML/s`$. After deposition is complete, a relaxation period with $`R_d=0`$ of about $`10^7`$ diffusion steps follows, corresponding to a physical time on the order of $`0.3s`$.

As we have demonstrated in , strain relaxation through dislocations is not expected for, say, $`ϵ=4\%`$ within the first few adsorbate layers. Indeed misfit dislocations were observed in none of the simulations presented here. Results have been obtained on average over at least 15 independent simulation runs for each data point.

In our simulations we observe the complete scenario of SK-like growth as described in the introduction. Illustrating mpeg movies of the simulations are available upon request or directly at our web pages . A section of a simulated crystal after deposition and island formation is shown in Figure 2. Ultimately, the formation of islands is driven by the relaxation of strain. As shown in the figure, material within the 3D-island and at its surface can assume a lattice constant close to that of bulk adsorbate. On the contrary, particles in the WL are forced to adapt the substrate structure.

During deposition, monolayer islands located on the WL undergo a rapid transition to bilayer islands at a well-defined thickness $`h_{\mathrm{WL}}^{}`$. For the systematic determination of $`h_{\mathrm{WL}}^{}`$ we follow  and fit the density $`\rho `$ of 3D-islands as $`\rho =\rho _o(hh_{\mathrm{WL}}^{})^\alpha `$, finding comparable values of the exponent $`\alpha `$. Figure 3 displays the results for two different substrate temperatures $`T`$ and various deposition rates $`R_d`$. The increase of $`h_{\mathrm{WL}}^{}`$ with decreasing $`T`$ agrees qualitatively with several experimental findings, see  as one example. Heyn discusses the effect of adsorbate/substrate interdiffusion on the $`T`$-dependence of $`h_{\mathrm{WL}}^{}`$ in the InGaAs system . Reassuringly, our result is consistent with his findings for absent intermixing.

A key observation is the significant increase of $`h_{\mathrm{WL}}^{}`$ with increasing deposition flux. Qualitatively the same flux dependence is reported for InP/GaAs heteroepitaxial growth in . This behavior leads to the conclusion that the emergence of islands upon islands, i.e. the SK-transition, is mainly due to particles performing upward hops onto existing monolayer islands. If, on the contrary, the formation of second or third layer nuclei by freshly deposited adatoms was the dominant process, one would expect more frequent nucleation and an earlier 2D-3D transition at higher growth rates. Note again that we have suppressed the ES-effect explicitly which would also lead to more frequent mound formation at higher deposition rates .

In our model, upward diffusion is the limiting effect and sets the characteristic time for the SK-transition. The frequency of these processes strongly depends on the temperature and it has to be compared with the deposition rate. A high incoming flux will fill layers before particles can perform upward hops, and hence it will delay the 2D-3D-transition, cf. 3. These considerations, together with the arguments of , suggest a functional dependence of $`h_{\mathrm{WL}}^{}`$ on $`F`$ and $`T`$ of the form

$$h_{\mathrm{WL}}^{}=h_o\left(\frac{F}{R_{up}}\right)^\gamma ,$$
(3)
where $`R_{up}`$ is the Arrhenius rate for upward hops. In our simulations we find a typical value which corresponds to an activation barrier $`E_{up}1.0eV`$ close to the transition. Using this value we have performed a non-linear fit according to Eq. (3) based on the data for $`T=500K`$. Inserting the obtained parameters $`h_o3.0ML`$ and $`\gamma 0.2`$ in Eq. (3) yields good agreement for $`T=480K`$, as well. Note that the value of $`\gamma `$ is expected to vary with the material system in the range $`0<\gamma <0.5`$ according to .

Our assumption that upward diffusion is more important than nucleation of deposited adatoms on top of islands is further supported by the observation that multilayer islands tend to form on a WL of, say, two monolayers thickness even without particle deposition.

After the 2D-3D-transition, islands grow by incorporating newly deposited material, but also by consumption of the surrounding WL. Note that very large islands are observed to split by means of upward diffusion events onto their top layer . The migration of WL particles towards and onto the islands can also extend into the relaxation period after deposition ends. Eventually, a stationary WL thickness $`h_{\mathrm{WL}}1`$ is observed in our example scenario with $`U_{as}0.86eV`$. By increasing the strength of the adsorbate/substrate interaction we can achieve, e.g., $`h_{\mathrm{WL}}2`$ for $`U_{as}2.7eV`$, but it is difficult to stabilize a greater stationary thickness, due to the short range nature of the LJ-potential.

Finally, we discuss the properties of 3D-islands emerging in SK-growth. As an example, their base length $`b`$ is measured as the number of particles in the island bottom layer. The results discussed in the following were obtained at the end of the relaxation period with $`R_d=0`$. Whereas mean values do not change significantly, fluctuations are observed to decrease with time in this phase.

We observe that, for fixed temperature, the island size decreases with increasing deposition flux, as observed in several experimental studies . However, $`b`$ becomes constant and independent of $`T`$ for large enough deposition rate, cf. Figure 4. A corresponding behavior is found for the island density and their lateral distance, hinting at a considerable degree of spatial ordering . The saturation behavior further demonstrates the importance of upward hops vs. aggregation of deposited particles on islands. The latter process would yield a continuous increase of the island density with $`R_d`$.

We find a narrower distribution of island sizes with increasing $`R_d`$ . The island size distribution in the saturation regime will be studied in greater detail in forthcoming investigations.

We conclude our discussion by noting that, in the saturation regime of high growth rates, the typical island size follows a simple power law: $`b1/ϵ`$, cf. Figure 4. Very far from equilibrium, the only relevant length scale in the system is given by the relative periodicity $`1/ϵ`$ of the adsorbate and substrate lattices. This characteristic length was already found to dominate in the formation of misfit dislocations for larger values of $`ϵ`$ .

## 5 Conclusion and Outlook

Despite its conceptual simplicity and the small number of free parameters, our model reproduces various phenomena of heteroepitaxial growth. We believe that, with a proper choice of interaction parameters, our model should be capable of reproducing all three prototype growth modes: layer by layer growth (for very small misfits), Volmer-Weber (for $`U_{as}<U_a`$) and, as demonstrated here, the Stranski-Krastanov mode. Our work provides a fairly detailed and plausible picture of the latter. The key features are:
(a) The strong adsorbate/substrate interaction favors the WL formation and results in a relatively slow diffusion of adatoms on the substrate. Diffusion on the WL is significantly faster and the corresponding barrier decreases with the WL thickness.
(b) Strain relaxation leads to a pronounced bias towards the island center on top of finite mono- and multilayer islands located on the WL. In addition, diffusion is slower on top of the partially relaxed islands than on the WL, in our model.

Whereas (a) favors the formation and persistence of the WL, (b) clearly de-stabilizes layer by layer growth. We find that the microscopic process which triggers the transition is upward diffusion of adatoms from the WL and at island edges. The corresponding barriers decrease with the WL thickness analogous to (a). As a result of the competing effects, the 2D-3D-transition occurs at a critical thickness which depends upon $`T`$ and $`R_d`$ as suggested in Eq. (3).

We hypothesize that strain effects induce spatial modulations with a characteristic length scale $`ϵ^1`$ and thus control the island size far from equilibrium. We find a corresponding saturation regime for large enough deposition fluxes. The precise mechanism of the size selection will be the subject of a forthcoming project. A related open question concerns the crossover from kinetically controlled island sizes to the equilibrium behavior which should be achieved in the limit of very small $`R_d`$. Several arguments  suggest that the typical island size close to equilibrium should be of order $`ϵ^2`$.

Further investigations will concern the effects of intermixing and segregation which have been excluded from our model, so far. To this end we will consider the co-deposition of both species and allow for exchange diffusion at the substrate/adsorbate interface.

In order to test the potential universality of our results, we will introduce different types of interaction potentials in our model. Ultimately, we plan to extend our model to the relevant case of $`2+1`$ dimensions and to more realistic empirical potentials for semiconductor materials, e.g. .

### Acknowledgment:

F. Much has been supported by the Deutsche Forschungsgemeinschaft. M. Biehl thanks the organizers and all participants of the NATO ARW on Quantum Dots: Fundamentals, Applications, and Frontiers  for pleasant and useful discussions. We also thank B. Voigtländer for communicating the results of  prior to publication.