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# Inhomogeneous magnetism in decagonal Al69.8Pd12.1Mn18.1

## .1 Introduction

Since the discovery of quasicrystalline systems by Shechtman et al. in 1982Shechtman et al. (1984), substantial progress in the understanding of quasicrystalline structures has been madeBeeli and Horiuchi (1994); Steurer et al. (1994); Boudard et al. (1992). Quasicrystalline structures are characterised by a high degree of atomic order, resulting in well defined X-ray and electron diffraction peaks, but they lack translational periodicity. This complicates the understanding of the electronic structure and hence of some important physical properties. The unusual electronic transport properties are often traced back to the formation of a pseudogap in the excitation spectrum at the Fermi levelTang et al. (1997); Giann$`\stackrel{`}{\mathrm{o}}`$ et al. (2001). The non-periodicity of the crystal lattice is the reason for special features in the temperature dependence of the thermal conductivity, reflecting a general type of Umklapp scatteringGiann$`\stackrel{`}{\mathrm{o}}`$ et al. (2001); Kalugin et al. (1996); Chernikov et al. (1996); Kalugin and Katz (1993). The quasiperiodic atomic arrangement is expected to also influence the magnetic features of quasicrystals (QCs), and in recent years, studies of magnetic properties of QCs have been in the focus of a number of research projects. While the initial studies were mainly performed on metastable Al-Mn QCs McHenry et al. (1988); Warren et al. (1986), a lot of progress has been made since then in preparing stable high-quality ternary QCs with local magnetic moments in alloy systems such as Al-Pd-Mn or Al-Mn-Ge. Depending on structure and stoichiometry, these QCs exhibit ferromagnetismYokoyama and Inoue (1996), diamagnetismHippert et al. (1996), paramagnetismGavilano et al. (2002); Dolin$`\stackrel{ˇ}{\mathrm{s}}`$ek et al. (2001) or spin-glass phenomenaFujimaki et al. (1991); Chernikov et al. (1993); Lasjaunias et al. (1995). Other intensively investigated families of magnetic QCs include Al-Cu-Fe and Al-Co-Ni alloysYamamoto et al. (1990), and the more recently synthesized quasicrystalline compounds containing rare-earth (RE) ions, such as RE-Mg-Zn with well localized $`4f`$-electron momentsFisher et al. (1999); Sato et al. (2000); Giann$`\stackrel{`}{\mathrm{o}}`$ et al. (2000); Wessel et al. (2002).

Several studies of the $`d`$-electron magnetism of Mn in icosahedral samples of Al-Pd-Mn have been motivated by the early discovery of the stable icosahedral $`i`$-Al-Pd-Mn phase. In spite of the above mentioned variety of magnetic properties found in these QCs, they seem to exhibit the common feature of only a small fraction of the manganese ions carrying a magnetic momentGavilano et al. (2002); Chernikov et al. (1993). In some cases this fraction even seems to decrease with decreasing temperatureGavilano et al. (2002). Theoretical studies and band-structure calculations aimed at explaining the phenomenon that only a fraction of the Mn ions carries a magnetic momentde Laissardiere and Mayou (2000), and to relate it to the Hume-Rothery type pseudo gap in the electronic spectrum around the Fermi levelHafner and Kraj$`\stackrel{ˇ}{\mathrm{c}}\stackrel{´}{\mathrm{i}}`$ (1998).

In comparison with the icosahedral Al-Pd-Mn alloys, the situation is less clear for decagonal Al-Pd-Mn alloys. For the latter, a larger number of sites has been predicted to carry a moment which, however, is smaller than the Mn moment established in icosahedral compoundsHafner and Kraj$`\stackrel{ˇ}{\mathrm{c}}\stackrel{´}{\mathrm{i}}`$ (1998). The present work reports the results of measurements of the dc magnetic susceptibility and of 27Al- and 55Mn-NMR studies of the decagonal QC $`d`$-Al69.8Pd12.1Mn18.1. From our results we infer that the Mn-moments in this compound are distributed very inhomogeneously. In the paramagnetic state and above 100K, only about half of the Mn ions carry a magnetic moment. The data also indicate that the fraction of Mn moments may even decrease upon reducing the temperature below 100K. Finally we confirm the previously reported spin-glass transition at $`T_f=12`$KChernikov et al. (2000).

## .2 The Sample

A metastable icosahedral sample of Al-Pd-Mn was obtained by spinning a melt of the stoichiometric composition of the decagonal phase Al69.8Pd12.1Mn18.1 onto a fast turning (30m/s), water cooled Cu wheel. Annealing the resulting tapes with the icosahedral phase for 100 hours at about 820C transforms them into polycrystalline flakes of the stable decagonal phaseBeeli et al. (1995). Decagonal Al-Pd-Mn has a columnar structure arranged on a two-dimensional quasiperiodic lattice. The translational period of length $`d=12.56\mathrm{\AA }`$ is built up by two different types of layers: a puckered layer P and a flat layer FSteurer et al. (1994). The ratio of Al in P to Al in F is approximately 2:1; for Mn this ratio is about 1:8Beeli and Horiuchi (1994).

High resolution transmission electron microscopy confirmed that our sample consists of polycrystalline $`d`$-Al69.8Pd12.1Mn18.1 with no linear phason strains. Selected area electron diffraction from room temperature down to below 30K proved the high perfection of the decagonal symmetry in the planes and the periodicity along the $`c`$-axis(see figure 1). Scanning electron microscopy sets the upper limit of the admixture of a second phase, i.e., Al11(Mn,Pd)4 on the surface of the back side of the tapes, to about 1%.

## .3 Experimental Results and their Analysis

### .3.1 Magnetic Susceptibility

We measured the dc-susceptibility $`\chi (T)`$ of $`d`$-Al69.8Pd12.1Mn18.1 with a dc-SQUID magnetometer between 340K and 2K, and at different magnetic fields between 50G and 5.5T. Figure 2 shows the inverse susceptibility $`1/(\chi (T)\chi _0)`$ measured at 500G between 5K and 350K. As may be seen in the inset of figure 2, field-cooled (FC) and zero-field cooled (ZFC) data differ below $`T_f12`$K. There is a well-defined maximum for the ZFC $`\chi (T)`$ at $`T_f`$. This behaviour confirms a spin-glass type freezing of the Mn-moments, previously claimed from the analysis of ac-susceptibility and specific-heat results measured on the same sampleChernikov et al. (2000). Above 120K, $`\chi (T)`$ may be approximated by $`\chi (T)=C/(T\mathrm{\Theta })+\chi _0`$ with

$$C=N_Acp^2\frac{\mu _B^2}{3k_B},$$
(1)
where $`N_A`$ is Avogadro’s number, $`c`$ the concentration of magnetic ions, and $`p`$ their effective moment $`p=g(JLS)\sqrt{J(J+1)}`$. The susceptibility data in the temperature range between 120K and 350K are best approximated with the parameters $`C=0.544`$\[emu/mol\], $`\mathrm{\Theta }=20`$K, and $`\chi _0=2.4510^8`$\[emu/g\].

The negative paramagnetic Curie temperature $`\mathrm{\Theta }`$ indicates a predominant antiferromagnetic coupling between the Mn $`d`$-moments. The Curie constant $`C`$ implies that $`p\sqrt{c}=2\pm 0.1\mu _B`$ per Mn-atom. This is not compatible with the assumption that all Mn ions adopt a well-defined and identical ionic configuration. If we assume, for example, localized Mn moments, our result for $`\chi (T)`$ imply a concentration of only 16.5$`\pm `$0.5% of Mn3+, or 12.5$`\pm `$0.5% of Mn2+. As we shall see in section .3.2, however, about half of the Mn ions carry a magnetic moment, and the distribution of the magnetic sites in $`d`$-Al-Pd-Mn is very inhomogeneous. Distinct deviations of $`\chi (T)`$ from the Curie-Weiss behaviour below 60K(see main frame of figure 2) signal precursor effects of the spin-glass freezing of the Mn moments.

Below 50K the susceptibility is field-dependent in fields below 5T. Figure 3 displays the magnetization $`M(H)`$ measured at various temperatures. As expected from the $`\chi (T)`$ data there is a hysteresis at 5K, due to ”memory effects” in the spin-glass phase. There is no visible hysteresis in the magnetization loop at 10K, suggesting that the relaxation of the magnetization at that temperature is faster than the time scale of the stepwise variation of the applied magnetic field in our experiments.

### .3.2 NMR spectra

We recorded 27Al and 55Mn NMR spectra between room temperature and 8K and at the frequencies of 21, 25, 30, 58, and 70MHz, using standard $`\pi /2`$-$`\tau `$-$`\pi `$ spin-echo sequences. Figure 4 shows two spectra recorded at 79 and 140K, respectively, with an excitation frequency of 24.97MHz. The NMR signal is distributed over a wide range of resonant fields from 2.1 to 2.4T. The prominent peaks near 2.25T represent the central 27Al Zeeman transition ($`1/21/2`$). The broad distribution of quadrupolar wings is a generic feature of QCsGavilano et al. (1997). The vertical dotted line in Figure 4 indicates the position of the resonance of 27Al nuclei in an aquaeous AlClO3 solution at room temperature and 24.97MHz, which is used as a reference signal. The solid lines represent the results of a computer simulation of the spectra which is described below.

The 27Al central transition is very broad, almost a factor of 10 broader than expected from considering the second order quadrupolar perturbation of the Zeeman line and than the analogous signals observed for the case of the non-magnetic Al-Pd-Re-compoundsGavilano et al. (1997). The line-width increases with decreasing temperature and, as we shall see below, the peculiar shape of the central line does not arise from anisotropies in the Knight-shift or quadrupolar effects. We argue that this signal consists of two partially resolved contributions representing the central transitions of Al nuclei located in either of two distinctly different local environments. One of the contributions, denoted as line I in figure 4, has very small or zero line-shift, while the other, denoted as line II in figure 4, exhibits a relatively large and $`T`$-dependent negative shift.

In order to confirm this conjecture we have looked for and found appreciable differences in the spin-spin relaxation for the 27Al nuclei that were allocated to different environments. This was achieved by changing $`\tau `$ in the $`\pi /2\tau \pi `$ echo sequence. Figure 5 displays two spectra recorded at 24.97MHz and 96K with two different values for $`\tau `$. The spectrum with $`\tau =30\mu `$s shows a distinct shoulder on the high-field side while in the spectrum with $`\tau =180\mu `$s this feature is clearly absent. In the upper inset of figure 5 we display the difference of the two spectra after taking into account $`T_2^{}`$-effects ($`1/T_2^{}=1/T_1+1/T_21/T_2`$). These effects affect both, line I and line II, which experience a suppression of signal intensity due to transverse relaxation processes. The loss of signal due to these processes has been taken into account by weighing factors obtained from a fit of $`Ae^{\frac{2\tau +d_2}{T_{2,\mathrm{I}}^{}}}+Be^{\frac{2\tau +d_2}{T_{2,\mathrm{II}}^{}}}`$ to the echo intensity as a function of $`\tau `$, with $`d_2`$ as the duration of the $`\pi `$-pulse. The thus obtained difference of the two spectra then reveals a clear manifestation of line II. The solid lines in the inset as well as in the main frame display the results of computer simulations, briefly discussed below. We conclude that the agreement between the experimental data and the calculated curves provides strong evidence for the existence of two different types of environments for the Al nuclei, giving rise to signals I and II, respectively.

Support for our claims is obtained from the results of our computer simulations of NMR spectra measured in a wide range of $`T`$-, $`H`$\- and $`\tau `$-values. The NMR frequency of a nucleus depends on the local magnetic field and on the local electric field gradient at the position of the nucleus, such that

$$\nu =\nu _\mathrm{L}\nu _\mathrm{Q}(m\frac{1}{2})\frac{3\mathrm{c}\mathrm{o}\mathrm{s}^2\theta 1}{2},$$
(2)
where $`\nu _\mathrm{L}`$ and $`\nu _\mathrm{Q}`$ denote the Larmor and the quadrupolar frequency, respectively, $`m`$ is the $`z`$-component of the upper nuclear spin state of the transition, and $`\theta `$ is the angle between the principal axis of the field gradient with respect to the local magnetic field at the position of the nucleus. We assumed that the Larmor frequencies $`\nu _\mathrm{L}`$ obey a Gaussian distribution whose width $`w`$ is caused by a ($`T`$-dependent) distribution of shifts, centered around $`\nu _0`$. Our previous attempts for fitting the – much simpler – 27Al-spectra of non-magnetic icosahedral quasicrystals of the Al-Pd-Re-family were successful when choosing the quadrupolar frequency $`\nu _\mathrm{Q}`$ to be uniformly distributed between some hundred kilohertz and a few megahertz. In the simulated 27Al-spectra of the present work, this distribution of $`\nu _\mathrm{Q}`$ ranges from 200kHz to 2MHz. The experimental spectra were successfully fitted by assuming two different sets of environments, characterized by two Gaussian distributions with different widths, $`w_\mathrm{I}`$ and $`w_{\mathrm{II}}`$, spread around two different central frequencies $`\nu _{0,\mathrm{I}}`$ and $`\nu _{0,\mathrm{II}}`$. The distribution of $`\nu _\mathrm{Q}`$ cited above was assumed to be the same for both environments. Figure 6 shows the calculated three contributions to the total spectrum, i.e., line I and line II of 27Al in the two different environments, and the signal originating from nuclei of non-magnetic Mn ions(discussed below). In order to compare the simulated spectra with the experimental data, the frequencies were translated into the corresponding applied fields. The distribution of angular orientations of the local quadrupolar axes was assumed to be random, because we used a polycrystalline sample.

### .3.3 NMR line shifts and widths

We determined the shift $`\mathrm{\Delta }H_{\mathrm{II}}`$ of line II by means of both, computer simulations of signals obtained with $`\tau =30\mu `$s, and also by subtracting the spectrum monitored with a long $`\tau `$ from that recorded with a short $`\tau `$, both at the same temperature, of course. Figure 7 shows the relative line-shift $`K_{\mathrm{II}}:=\mathrm{\Delta }H_{\mathrm{II}}/H`$ of line II as a function of temperature. The open symbols indicate the values obtained by subtraction, the closed symbols correspond to values obtained by computer simulations. The absolute line shifts $`\mathrm{\Delta }H`$ scale linearly with field and can be expressed by

$$K:=\frac{\mathrm{\Delta }H}{H}=K_{\mathrm{ce}}+K_{\mathrm{mag}}(T),$$
(3)
where $`K_{\mathrm{ce}}`$ is a temperature-independent contribution, which in our case is much larger in magnitude than those found in non-magnetic quasicrystalsGavilano et al. (2002, 1997); Apih et al. (2000). Temperature-independent NMR line-shifts can be caused by a variety of processes, however, $`K_{\mathrm{ce}}`$ of line II is too large to be attributed to typical chemical shifts or to quadrupolar effects. Therefore one is tempted to associate $`K_{ce}`$ with the paramagnetism of the conduction electrons. In common metals this contribution, the Knight shift, is positive, but, in our case $`K_{ce}`$ is negative. A negative and temperature-independent line shift cannot be caused by conduction electrons originating from the Al $`s`$ and $`p`$ shells but may be due to itinerant electrons originating from the Mn $`d`$-shellClogston et al. (1964); Carter et al. (1977). The Pd $`d`$-band is full and therefore these states are not expected to contribute significantly to the resonance shift. Such an interpretation is compatible with recent experimental results concerning the electronic structure of Al-Pd-Mn quasicrystals Erbudak et al. (2001). Nevertheless, the origin of the negative Knight-shifts, also found in other quasicrystals, is still an open question. For line I the relative shift $`K`$ is also negative but less than 100ppm. The existence of two distinct lines with different shifts therefore strongly suggests that the conduction electron density at the 27Al nuclei is not uniform. In some regions, which contribute to the intensity of line II, there is a substantial conduction electron density and, as we argue below, the Mn ions in that region are magnetic. In other regions, which contribute to the intensity of line I, the conduction-electron density is reduced and the Mn ions are non-magnetic.

$`K_{\mathrm{mag}}(T)`$, only clearly observed for line II, exhibits a Curie-Weiss type behaviour in the whole temperature range covered by the data shown in figure 7. The paramagnetic Curie-temperature $`\theta =6`$K is in fair agreement with the value obtained from fits to the susceptibility. The inset of figure 7 displays the line-shift data plotted versus the dc-susceptibility measured in different fields. It confirms that $`K_{\mathrm{mag}}(T)`$ may be written as

$$K_{\mathrm{mag}}(T)=A\chi (T).$$
(4)
The proportionality constant $`A`$ is a measure of the average coupling strength of the 27Al nuclear spins to the Mn magnetic moments. For metals, $`A`$ is usually written as

$$A=\frac{1}{\mu _BN}H_{\mathrm{eff}},$$
(5)
with $`H_{\mathrm{eff}}`$ as the hyperfine field from each aligned Bohr magneton. $`N`$ is Avogadro’s numberCarter et al. (1977). In our case, where only a fraction $`c`$ of the Mn ions is magnetic and because the molar susceptibility is calculated per total Mn content, equation (5) has to be changed to

$$A=\frac{1}{\mu _BcN}H_{\mathrm{eff}}.$$
(6)
In spite of the large error bars, our data suggest that there are two temperature regimes with different values of $`A`$, below and above approximately 110K. This change may simply reflect a reduction of the fraction of magnetic Mn moments $`c`$. This interpretation gains support from the 55Mn NMR spectra, where we observe that the intensity of the non-magnetic Mn line is 35% and 50% of the total expected Mn intensity above and below 100K, respectively. However, other processes leading to a change in the hyperfine coupling cannot be ruled out.

The widths of both lines increase with decreasing temperature and therefore give a clear indication that they are both of magnetic origin. Also line I is much broader than the central 27Al line in other Al-Pd-Mn compoundsGavilano et al. (2002), suggesting that the regions of the two environments mentioned above are finely dispersed in the bulk of the sample. At this point we focus our attention on line II, where the influence of the Mn moments is particularly pronounced. In figure 8 the temperature dependence of the ratio $`w_{\mathrm{II}}/\nu _{\mathrm{irrad}}`$, where $`w_{\mathrm{II}}`$ is again the width of line II and $`\nu _{\mathrm{irrad}}`$ the corresponding irradiation frequency, is plotted for four different irradiation frequencies, i.e., four different average applied fields. Since all the data fall onto a single curve, it follows that the line-width scales with the irradiation frequency, or, equivalently, with the applied magnetic field and, therefore, must be of magnetic origin. The enhancement with decreasing temperature occurs with increasingly negative slope. The inset of figure 8 displays the same data plotted versus the dc-susceptibility measured at similar fields. The width of line II originates from a distribution of shifts of the 27Al nuclei around an average shift. The slope of that curve therefore is a measure of the width of the distribution of the site dependent coupling strengths $`A(𝐫)`$ between the Al nuclear spins of line II and the Mn moments, with respect to the total magnetic susceptibility, which is mainly due to localized Mn moments. It shows a pronounced change at approximately 110K. Such a slope change could be induced by a reduction of the number of magnetic Mn ions, leading to a reduced increase in the susceptibility.

The NMR spectra recorded at a chosen frequency reveal some additional intensity at a field where one expects the 55Mn signal at zero shift. This is most clearly seen near 5.5T in figure 6. Since the hyperfine field coupling of the Mn moment to the nucleus of the same ion is through the core-polarization, which is of the order of -100kG/$`\mu _\mathrm{B}`$ for MnWarren et al. (1986), even a small moment on a Mn ion would shift its resonance frequency by several MHz. Therefore this signal intensity in our spectra must originate from non-magnetic Mn atoms (see figure 6). From the spectra recorded at 70MHz, where the Mn-signal is clearly resolved, we conclude that the fraction of Mn-atoms carrying no magnetic moment is of the order of 45$`\pm `$15%. We note that this value is not far from the ratio of the intensities of line I and II which was found to be $`0.4\pm 0.1`$. Thus we may again conclude that the Al lines I and II arise from Al nuclei in the neighborhood of nonmagnetic and magnetic Mn ions, respectively. Considering the average moment of $`p=2\pm 0.1\mu _B`$, deduced from the dc molar susceptibility data with respect to the total Mn content, we estimate that the average effective moment per magnetic Mn ion is $`p=3\mu _B`$, if we assume that 45% of the Mn ions actually are magnetic. This number is not compatible with any of the possible ionization states of Mn, which would lead to $`p=4\mu _B`$ for Mn4+, $`p=5\mu _B`$ for Mn3+, and $`p=5.9\mu _B`$ for Mn2+.

### .3.4 NMR Spin-lattice relaxation rate

We measured the spin-lattice relaxation rate $`T_1^1`$ of line I from room temperature down to 15K in three different applied fields. The values of $`T_1`$ were extracted from fits to the nuclear magnetization recovery $`m(t)`$, which was first destroyed using a long comb of rf-pulses, followed by a variable delay $`t`$ and a spin-echo sequence $`\pi /2\tau \pi `$ with a long $`\tau =180\mu `$s. In this manner it is possible to identify exclusively the spin-lattice relaxation rate related to line I. Using shorter values of $`\tau `$ in these measurements leads to changes in $`m(t)`$ which, in our view, results in less reliable values of $`T_1`$. According to standard NMR theory, the signal intensity of the central line of a spin $`I=5/2`$ nucleus relaxes such thatNarath (1967):

$$1m(t)/m(\mathrm{})=0.4762e^{15t/T_1}+0.2667e^{6t/T_1}+0.2571e^{t/T_1}.$$
(7)
Even for line I alone, there is no distinct single Al-site, but rather a variety of sites leading to a distribution of $`T_1`$’s. Since the details of the distribution of $`T_1`$’s are not known, we simply model $`m(t)`$ by replacing the exponentials by stretched exponential functions111We found good agreement between equation (8) and magnetization recoveries obtained by computer simulations of a collection of ensembles with different $`T_1`$.:

$$1m(t)/m(\mathrm{})=0.4762e^{15(t/T_1)^\beta }+0.2667e^{6(t/T_1)^\beta }+0.2571e^{(t/T_1)^\beta }.$$
(8)
Figure 9 displays an example of a magnetization recovery at a relatively low temperature and the corresponding best fit to the data using equation (8). With an increasing pulse separation $`\tau `$ in the echo sequence the exponent $`\beta `$ converges to an approximate value of 0.9. Therefore, in the subsequent analysis we set $`\beta =0.9`$. As may be seen in the inset of figure 9, also the $`T_1`$ values turned out to vary with $`\tau `$ but to reach a constant value for $`\tau 180\mu `$s. Therefore, we fixed $`\tau `$ to $`180\mu `$s for all the measurements of $`T_1`$ discussed below.

Figure 10 displays $`T_1^1(T)`$ obtained from fitting the data obtained at three different fields of 5.2T, 2.25T, and 1.85T, with $`\tau =180\mu `$s to equation (8). Below 50K the spin-lattice relaxation rate increases with an increasingly negative slope as $`T`$ approaches the spin-glass freezing temperature $`T_f`$. This behaviour is typical for nuclear spins which experience the influence of magnetic moments that undergo a gradual slowing down of their fluctuations. In the present case, the Mn moments, although predominantly affecting line II, are also felt in the relaxation of the nuclear spins contributing to line I, as the spin-glass transition is approached upon cooling. At high temperatures, the spin-lattice relaxation rate of non-magnetic nuclei due to paramagnetic centers is given byAbragam (1994):

$$\frac{1}{T_1}=C\frac{\tau }{1+\omega _I^2\tau ^2}.$$
(9)
$`C`$ is proportional to the hyperfine-field coupling between the Mn moments and the Al nuclei, $`\tau `$ is the correlation time of the Mn moments, and $`\omega _I=2\pi \nu _{0,\mathrm{I}}`$ is the Larmor precession frequency of the nucleus under investigation222Equation (9) is a high-temperature approximation where the correlations among the paramagnetic moments are neglectedAbragam (1994).. In the fast-motion regime, at temperatures much higher than $`T_f`$, $`\omega _I^2\tau ^2`$ is much smaller than 1 and the relaxation rate is temperature- and field-independent. As $`T`$ is reduced towards $`T_f`$, the moment fluctuations slow down and cause an increase of $`T_1^1`$($`\tau `$), as observed below 50K. The $`\tau `$-driven increase can be understood by assuming that $`\omega ^2\tau ^2`$ is still much less than 1, which is implicitly confirmed by the almost $`H`$-independent increase of $`T_1^1(T)`$ below 50K. Close to $`T_f`$, the growing linewidth usually prohibits to extract reliable $`T_1`$ values. In our case this is true for $`T<20`$K.

The $`T_1^1(T)`$ plot in figure 10 exhibits a broad maximum centered around 120K. This maximum is very unusual and has – to our knowledge – never been seen in $`T_1^1(T)`$ of any other quasicrystalline compound. The spin-lattice relaxation rate usually contains three contributions

$$T_1^1=T_{1,\mathrm{ce}}^1+T_{1,\mathrm{mag}}^1+T_{1,\mathrm{q}}^1.$$
(10)
The total relaxation is characterized by $`T_{1,\mathrm{ce}}^1`$, due to conduction electrons, $`T_{1,\mathrm{mag}}^1`$ reflecting the relaxation due to the paramagnetic centers, and $`T_{1,\mathrm{q}}^1`$ capturing the quadrupolar relaxation. In a simple metal, $`T_{1,\mathrm{ce}}^1`$ is known to vary linearly with temperature. In quasicrystals the relaxation due to itinerant electrons depends on the shape of the density of states at the Fermi level and thus on the shape of the pseudogap. A power-law or polynomial increase of the spin-lattice relaxation rate with rising temperature is expectedTang et al. (1997); Gavilano et al. (1997). It may be seen in figure 10 that above 175K the $`T`$-dependence of the spin-lattice relaxation rate may well be dominated by conduction electrons and they still contribute significantly to the total $`T_1^1`$ in the crossover regime around 120K. However $`T_{1,\mathrm{ce}}^1`$ cannot account for the maximum at 120K, unless some anomaly in the electronic excitation spectrum causes the feature at that temperature. Major changes in $`T_{1,\mathrm{ce}}`$ around 120K are, however, not to be expected because the monotonous variation of the electrical resistivity with temperature, shown in figure 11, does not support a corresponding feature in the electronic excitation spectrum that would cause the anomaly in $`T_1^1`$ around 120K.

Also any substantial contribution of $`T_{1,\mathrm{q}}^1`$ can be ruled out. The spin-lattice relaxation rate of Al nuclei is larger by more than a factor of 10 in $`d`$-Al-Pd-Mn than it is in $`i`$-Al-Pd-Re, where it is still dominated by $`T_{1,\mathrm{ce}}^1`$ and not $`T_{1_,\mathrm{q}}^1`$Tang et al. (1997). Hence $`T_{1,\mathrm{q}}^1`$ in $`d`$-Al-Pd-Mn is expected to be very small in comparison with other contributions, unless a major change of structure at some temperature occurs in that compound. Results of selected area electron diffraction (SAED) measurements from room temperature down to below 30K indicate that no structural changes occur in this temperature regime and therefore it may be concluded that $`T_{1,\mathrm{q}}^1`$ does not contribute significantly to changes in $`T_1^1(T)`$.

We are thus left with the second significant term in (10), i.e. $`T_{1,\mathrm{mag}}^1`$, which describes the magnetic interactions between the Al nuclear spins and the Mn $`d`$-moments. In our case, with $`\omega _\mathrm{I}\tau <<1`$ in equation equation (9), $`T_1^1`$ is expected to be almost $`T`$ and $`H`$independent. We note that the values of $`T_1^1`$ of other magnetic quasicrystals of the Al-Cu-Fe-familyTang et al. (1997); Dolin$`\stackrel{ˇ}{\mathrm{s}}`$ek and Klajn$`\stackrel{ˇ}{\mathrm{s}}`$ek (2001) and icosahedral samples of Al-Pd-Mn with lower Mn concentrationGavilano et al. (2002) are smaller than for the presently investigated material by at least one order of magnitude as well. This giant difference is mainly attributed to the larger contribution of $`T_{1,\mathrm{mag}}^1`$ to the total spin-lattice relaxation rate in the present case. Based on these arguments we suggest that the maximum in $`T_1^1(T)`$ is related to $`T_{1,\mathrm{mag}}^1(T)`$ and reflects the previously mentioned reduction of the concentration of magnetic Mn moments below approximately 100K.

In figure 12 we compare the low temperature 27Al spin-lattice ralaxtion rate of $`d`$-Al-Pd-Mn with those of 27Al nuclei in a non-magnetic $`i`$-Al-Pd-Re quasicrystalGavilano et al. (1997) and in $`i`$-Al-Pd-MnGavilano et al. (2002). In the covered temperature region the relaxation rates in both, the non-magnetic $`i`$-Al-Pd-Re as well as the weakly magnetic $`i`$-Al-Pd-Mn, are smaller by more than an order of magnitude and exhibit a distinctly different temperature dependence.

## .4 Summary

Our susceptibility data and our NMR spectra reveal that at elevated temperatures more than half of the Mn ions in decagonal Al69.8Pd12.1Mn18.1 carry a small magnetic moment, giving rise to an average Mn-moment of 2$`\mu _\mathrm{B}`$. These moments experience an average antiferromagnetic interaction, leading to a spin-glass freezing at $`T_f12`$K. We presented arguments that the number of these moments is gradually reduced below 100K. A similar reduction of moments was observed at lower temperatures in $`i`$-Al-Pd-Mn with a much smaller density of magnetic Mn momentsGavilano et al. (2002).

The 27Al NMR spectra show two partially resolved lines. Line II is clearly much more influenced by the Mn-magnetism. Similar line-shapes have been found in very early experiments on Mn-rich metastable Al-Mn quasicrystalsWarren et al. (1986), but they could not be resolved into two lines at that time. We argue that the two lines are due to Al on sites in environments favoring the formation of a magnetic moment on the Mn ions (line II) and to Al in an environment, where the Mn moments are quenched (line I). Our results strongly suggest that simple Al-$`p`$-Mn-$`d`$ hybridization alone may not adequately account for the phenomenon of Mn-magnetism in QC’s, but that a more subtle, conduction-electron mediated long-range mechanism has to be considered de Laissardiere and Mayou (2000).

We have not yet found an unequivocal interpretation for the broad maximum of $`T_1^1`$ at 120K. The same process that leads to that maximum seems to lead to a reduction of the fraction of Mn-ions that carry a magnetic moment, or, possibly an increased hyperfine coupling below 110K. Neither a structural transition nor a significant change in the electronic density of states is indicated by SAED and transport measurements, respectively.

## .5 Acknowledgement

We thank Ren$`\stackrel{´}{\mathrm{e}}`$ Monnier for fruitful discussions, Roland Wessiken for his help with the temperature-dependent selected area electron diffraction, and Matthias Weller for his assistance in the measurement of the electrical conductivity.


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# Conditional preparation of a quantum state in the continuous variable regime : generation of a sub-Poissonian state from twin beams

(Received: 16 April 2003 / Revised version: 12 September 2003)

## Abstract

We report the first experimental demonstration of conditional preparation of a non-classical state of light in the continuous variable regime. Starting from a non-degenerate OPO which generates above threshold quantum intensity correlated signal and idler ”twin beams”, we keep the recorded values of the signal intensity only when the idler intensity falls inside a band of values narrower than its standard deviation. By this very simple technique, we generate a sub-Poissonian state 4.4 dB (64%) below shot noise from twin beams exhibiting 7.5 dB (82%) of noise reduction in the intensity difference.

A well-known technique to generate a single photon state from quantum correlated photons (”twin photons”) is to use the method of conditional measurement: if one labels (1) and (2) the two modes in which the twin photons are emitted, it consists in retaining in the information collected on mode (1) only the counts occurring when a photon is detected in mode (2) (within a given time window $`\mathrm{\Delta }T`$). This method has been widely and very successfully used over the past decades, firstly with twin photons generated by an atomic cascade Aspect , then by using the more efficient technique of parametric down conversion fock1 . Various protocols have been proposed to use conditional preparation in order to generate other kinds of non-classical states, for example Schrödinger cat states using a squeezed vacuum state transmitted through a beamsplitter and a measurement conditioned by the counts detected on the reflected port cat . In a similar way, teleportation of a quantum state of light can be achieved by using conditional measurements teleport  and the degree of entanglement can be improved by photon subtractions improve . In cavity QED, conditional measurements on the atomic state have also led to the experimental generation of non-classical photon states haroche .

State reduction is obviously not restricted to the case of photon counting, so that it may be interesting to extend this technique to the continuous variable regime, where a continuously varying photocurrent is measured instead of a series of photocounts. Continuous detection conditioned by a photon counting event has been implemented in various schemes OrozcoSchiller . Closer to our proposal where continuous measurements are used both for triggering and characterizing the generated state, many theoretical protocols have been suggested relying on two-mode squeezed vacuum produced by a non-degenerate optical parametric amplifier reducetwins ; kumar . For instance, homodyne measurements on the idler can be used to condition the detection of the signal and would reduce it to a squeezed state reducetwins .

In a conditional state preparation, the generation of the non-classical state can be seen as the collapse of the entangled wave-function induced by the measurement on one of its components. However, very frequently, the measurement is made by post-selection of the relevant events in the record of all the values measured on the two channels, which can be made after the end of the physical measurement, so that no wave-function collapse actually occurs during the experiment. Note that, in contrast to the methods of direct generation of a non-classical state, the exact time window when the state is produced is not controlled in a conditional measurement, and what we will call the ”success rate”, i.e. the probability of generating the non-classical state in a given time interval, is an important parameter to characterize its efficiency.

To the best of our knowledge, no scheme has been suggested so far to generate non-classical intense beams by the technique of conditional measurement performed on continuous variables. This is the purpose of the present letter, which proposes a very simple way of conditionally preparing a bright sub-Poissonian beam from twin beams, and reports on its experimental implementation. The theory of the presented technique will be detailed in a forthcoming publication theory .

It is well known that a non-degenerate optical parametric oscillator (ND-OPO) produces above threshold intense signal and idler ”twin beams” traditional  : in the ideal case of a system without losses, the Fourier components of the signal and idler intensity quantum fluctuations which lie inside the cavity bandwidth are perfectly correlated. The correlations are characterized by the ”gemellity”, which is the remaining noise on the intensity difference between the signal and idler intensities normalized to the corresponding quantum noise level Reynaud . The instantaneous values of the signal and idler photocurrents play therefore the role of the occurrence of counts in the photon counting regime. The conditional measurement technique that we propose consists in selecting the signal photocurrent $`I_s`$ only during the time intervals when the idler intensity $`I_i`$ has a given value $`I_0`$ (within a band $`\mathrm{\Delta }I`$ smaller than the photocurrent standard deviation). The measurements outside these time intervals are discarded. If the correlation is perfect and the interval $`\mathrm{\Delta }I`$ close to zero, the recorded signal intensity is perfectly constant, and an intense number state is generated by this conditional measurement.

In a real experiment, the correlation between the signal and idler photocurrents is not perfect, and the selection band $`\mathrm{\Delta }I`$ is finite, so that the method will not prepare a perfect number state, but a sub-Poissonian state instead. The density matrix describing the state of light which is produced by such a state reduction technique can be determined within the approximation that the signal and idler photon distributions are Gaussian theory . In the limit where $`\mathrm{\Delta }I`$ is very small, one finds that, whatever the initial intensity noise of the beams are, the conditional measurement produces a sub-Poissonian signal beam, characterized by a Fano factor equal to the conditional variance of the intensity fluctuations of the signal beam knowing the intensity fluctuations of the idler beam, which plays an important role in the characterization of Quantum Non Demolition measurements grangier . In other words, in the limit of large correlations, the intensity noise reduction on the conditionally prepared state is equal to the twin beam noise reduction minus 3dB.

Obviously, if $`\mathrm{\Delta }I`$ is very small, the probability that the idler intensity lies within the chosen band is also very small, and the success rate of the non-classical state production by such a conditional measurement is also very low. Computer simulations, as well as analytical calculations theory , show that the Fano factor of the generated state remains almost constant in a wide range of $`\mathrm{\Delta }I`$ values, whereas the success rate of the method increases quickly. It is only when $`\mathrm{\Delta }I`$ reaches values comparable to the shot noise standard deviation that the post-selection process becomes less efficient, and the Fano factor tends to its uncorrected value.

The present conditional measurement technique has strong analogies with the method of active feed-forward correction of the signal beam intensity, by opto-electronics techniques, using the information obtained from the measurement of the idler intensity mertz1 ; mertz2 , which produces a sub-Poissonian state with a Fano factor also equal to the conditional variance. The present technique is much simpler to implement, whereas the active correction technique is non-conditional, and has the advantage of producing the non-classical state at all times.

The experimental setup is shown in Figure 1. A continuous frequency-doubled Nd:YAG laser pumps a triply resonant ND-OPO above threshold, made of a semi-monolithic linear cavity : in order to increase the mechanical stability and reduce the reflection losses, the input flat mirror is directly coated on one face of the 10mm-long KTP crystal. The reflectivities for the input coupler are 95.5% for the pump (532nm) and almost 100% for the signal and idler beams (1064nm). The output coupler (R=38mm) is highly reflecting for the pump and its transmission is 5% for the infrared. At exact triple resonance, the oscillation threshold is less than 15mW. The OPO is actively locked on the pump resonance by the Pound-Drever-Hall technique: we detect by reflection the remaining 12MHz modulation used in the laser to lock the external doubling cavity. In order to stabilize the OPO infrared output intensity, the crystal temperature has to be drastically controlled (within a mK). The OPO can operate stably during more than one hour without mode-hopping. The signal and idler orthogonally polarized beams (in the 1-5mW range) generated by the OPO are then separated by a polarizing beam-splitter and detected on a pair of balanced high quantum efficiency InGaAs photodiodes (Epitaxx ETX300, quantum efficiency: 95%). An half-wave plate is inserted before the polarizing beam-splitter. When the polarization of the twin beams is turned by 45 with respect to its axes, it behaves as a 50% usual beam-splitter, which allows us to measure the shot noise leveltraditional .

In almost all the bright twin beams experiments to date traditional , the photocurrents are subtracted and the difference is sent onto a spectrum analyzer which gives the variance of the photocurrent distribution. We have implemented a different protocol to have access to the full photon-number quantum statistics of the signal and idler beams at a given Fourier frequency $`\mathrm{\Omega }`$ (see also computer ): each photocurrent is amplified and multiplied by a sinusoidal current at frequency $`\mathrm{\Omega }`$ produced by a signal generator, and filtered by a 22kHz low-pass filter in order to obtain the instantaneous value of the photocurrent Fourier component at frequency $`\mathrm{\Omega }`$, which is then digitized at a sampling rate of 200 kHz by a 12-bit, 4-channel acquisition card (National Instruments PCI-6110E), which also simultaneously records the instantaneous values of the DC photocurrents. Two successive acquisitions (200 000 points for each channel) are required, one for calibrating the shot noise by rotating the half-wave plate and the other to record the quantum correlated signals.

Figure 2 sums up the measurements obtained with a demodulation frequency $`\mathrm{\Omega }/2\pi =3.5MHz`$. Figure 2a shows the actual recording of the fluctuations of the idler beam during a time interval of 100ms. As the OPO is pumped close to threshold, the signal and idler beams have intensity fluctuations which are much larger than the standard quantum limit, as can be seen on curve 2b, giving the probability distribution of the intensity fluctuations normalized to the shot noise. The corresponding Fano factor exceeds 100 (20 dB above the shot noise level). From the recorded data, one can calculate the noise variance on the difference between the signal and idler intensities. It reaches a value of 7.5 dB below the standard quantum limit (8.5 dB after correction of dark noise), in good agreement with the value of the noise variance measured on the spectrum analyzer. The dark noise, which is more than 6 dB below all measurements, is not subtracted in the following experimental results.

The conditional measurement is performed in the following way : the signal intensity values are kept only if the idler intensity values recorded at the same time fall inside a narrow band around its mean value. The remaining ensemble of values of the signal intensity is given in figure 2c, in which the shot noise is given at the same time : one indeed observes a significant narrowing of the probability distribution below the shot noise level. Let us stress that the shot noise is unchanged by this selection process: the beam exists only in the selection intervals so that the unselected intervals do not contribute to the average value. Figure 2d gives the probability distribution of the intensity fluctuations of the conditionally prepared state normalized to the shot noise, together with the Poissonian distribution of photons for the same mean intensity. With a selection bandwidth $`\mathrm{\Delta }I`$ equal to 0.1 times the standard deviation $`\sigma _0`$ of a coherent state having the same power (shot noise level), the conditionally prepared light state exhibits 4.4 dB of noise reduction below the Poisson distribution. This value is very close from the theoretical expectation in the case of vanishingly narrow intensity band. The success rate of the conditional preparation is around 0.85% (1700 points out of 200 000 are accepted). This value would be higher for an initial state with less excess noise above shot noise.

The success rate can be improved by increasing the selection bandwidth, at the expense of a decreased non-classical character of the selected state. Figure 3 shows the measured residual noise in the conditionally produced state, and the success rate of the state generation, as a function of the selection bandwidth normalized to the $`\sigma _0`$. The noise reduction turns out to be almost constant until the normalized selection bandwidth becomes of the order of 0.1, whereas the success rate steadily increases, in very good agreement with numerical simulations. However, one can see a slight increase in the noise when the selection bandwidth becomes very narrow. This artefact is due to the sampling process on a finite range of bits (12), which restricts the resolution of the acquisition.

In figure 4, we give the measured residual noise for different amounts of intensity correlations between the beams, which can be varied by inserting losses on the OPO beams. One checks on the figure the validity of the prediction that the noise reduction is equal to the gemellity minus 3dB. One also observes than, when the intensity difference noise is reduced by less than 3dB below the standard quantum level, the conditional state has reduced intensity noise fluctuations in comparison with the very noisy initial beam, but that it is not a non-classical sub-Poissonian state.

The continuous variable regime offers a unique possibility to improve dramatically the efficiency of conditional strategy, by choosing multiple selection bands with different mean values on the idler intensity. Independent selection bands will correspond to independent sets of time windows. By using hundreds of independent intervals, one keeps most of the values of the signal, each of these intervals reducing the signal to a given sub-Poissonian state. Figure 5 shows that the noise reduction does not depend of the band center and that the success rate follows the initial gaussian noise distribution.

To conclude, we have shown the first experimental demonstration of conditional preparation of a quantum state in the continuous variable regime. We have studied the influence of the selection bandwidth of the conditioning measurement on the obtained non-classical state and on the success rate of its preparation and shown that many sub-Poissonian states can be produced in parallel. This method to generate non-classical states of light in the continuous variable regime is equivalent to sending the signal beam through an intensity modulator which either totally transmits the beam when the idler beam has the right value, or blocks it when it is not the case. It therefore drastically changes the light state, and seems to be very different from the usual technique which consists of correcting the beam fluctuations by a feed-forward or feed-back opto-electronic loop which only slightly modifies the quantum fluctuations. This strongly non-linear character of the action on the light may lead to the generation of non-Gaussian states. One could also envision other criteria of conditioning the quantum state than simply imposing to the idler beam intensity to lie within a given band. This could also lead to the generation of new families of non-classical bright states of light.

###### Acknowledgements.

Laboratoire Kastler-Brossel, of the Ecole Normale Supérieure and the Université Pierre et Marie Curie, is associated with the Centre National de la Recherche Scientifique (UMR 8552). We acknowledge support from the European Commission project QUICOV (IST-1999-13071) and ACI Photonique (Ministère de la Recherche).


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# How to make semiconductors ferromagnetic: A first course on spintronics

## I introduction

The study of semiconductors (i.e. intrinsically insulating materials with band gaps in the $``$ 1 eV range) which are also ferromagnetic has a long, but perhaps somewhat intermittent, history. Back in the 1960s and early 1970s there was a great deal of interestNagaev (1983) in Eu-based chalcogenide materials which exhibited ferromagnetism with Curie temperature around 50K or less. These were strongly insulating systems with rather poor semiconducting transport properties. In the 1980s there were major effortsFurdyna (1988) in magnetically doped II–VI ternary and quarternary semiconductor alloys, e.g. CdMnSe, CdMnTe, PbSnMnTe *etc.*, but most of these materials exhibited spin glass or related disordered magnetic behavior and any ferromagnetism invariably had very low ($``$ 5K) transition temperature. The idea of a diluted magnetic semiconductor, where a small ($`<10\%`$) concentration of magnetically active atoms (most often Mn although Co and Cr have also been used occasionally) is distributed at the cation sites of the host semiconductor, is appealing because such a system may have both semiconducting and ferromagnetic properties. Making such materials has, however, been problematic because the magnetic transition metal (i.e. Mn) is not thermodynamically stable in the semiconductor host (e.g. GaAs), and tends to segregate.

The need for actively controlling and manipulating the carrier spin degree of freedom (in addition to the charge degree of freedom) in semiconductors leading to novel multifunctional magneto-opto-electronic capabilities has created the emerging interdisciplinary field of spintronics (or spin electronics). A key component of spintronics is the development of new ferromagnetic semiconductors. Following the successful development of Ga1-xMnxAs Ohno et al. (1996); Ohno (1998, 1999) and In1-xMnxAs Ohno et al. (1992) as ferromagnetic semiconductors (with $`x110\%`$) using careful low-temperature molecular beam epitaxy (MBE) technique, intensive worldwide activity has led to claims of ferromagnetism (some at room temperatures and above) in several magnetically doped semiconductors, e.g. GaMnP,Theodoropoulou et al. (2002) GaMnN,Reed et al. (2001) GeMn,Park et al. (2002) GaMnSb.Chen et al. (2002) It is at present unclear whether all these reports of ferromagnetism (particularly at room temperatures or above) are indeed intrinsic magnetic behavior or are arising from clustering and segregation effects associated with various Mn-complexes (which have low solubility) and related materials problems. The observed ferromagnetism of GaMnAs is, however, well-established and is universally believed to be an intrinsic diluted magnetic semiconductor (DMS) phenomenon.

The Mn dopants in GaMnAs serve the dual roles of magnetic impurities providing the local magnetic moments and of acceptors producing, in principle, one hole per Mn atom. The number density $`n_\text{c}`$ of the charge carriers (holes in GaMnAs), however, turns out to be by almost an order of magnitude lower than the number density $`n_\text{i}`$ of the Mn ions, making the system to be a highly compensated doped semiconductor. This high level of compensation is believed to be a crucial ingredient in the underlying DMS ferromagnetic mechanism. In particular, the precise role played by the relative values of the local moment density $`n_\text{i}`$ and the hole density $`n_\text{c}`$ in giving rise to DMS ferromagnetism is currently being debated in the literature to the extent that there is no agreement even on whether the heavy compensation ($`n_\text{c}n_\text{i}`$) in the system helps or hinders ferromagnetism. An important question in this context is to obtain the functional dependence of the ferromagnetic transition temperature (“Curie temperature”) $`T_c`$ on magnetic moment and hole densities $`n_\text{i}`$ and $`n_\text{c}`$. In Ga1-xMnxAs the early experimental results Ohno et al. (1996); Matsukura et al. (1998) indicated a nonmonotonic behavior of $`T_c(x)`$ with $`T_c`$ first increasing with the Mn concentration $`x`$, reaching a maximum of about 110K for $`x5\%`$, and then decreasing with further increase of Mn concentration above this optimum value. A strong correlation between the magnetic transition temperature and transport properties of GaMnAs was also reported in these findings Ohno et al. (1996); Matsukura et al. (1998) with the system exhibiting relatively stronger metallic behavior close to this optimum Mn doping level ($`5\%`$). Recent experimental studies Potashnik et al. (2001); Edmonds et al. (2002) of Ga1-xMnxAs under carefully controlled annealing conditions seem to suggest that the metastable nature (and high defect content) of low temperature MBE grown GaMnAs may be playing an important role in determining magnetic properties – in particular, careful annealing could, under suitable conditions, lead to an enhancement of $`T_c`$ with increasing Mn content leading to an eventual saturation of the transition temperature in the $`x=58\%`$ range without the nonmonotonic $`T_c(x)`$ behavior observed earlier. These annealing studies Potashnik et al. (2001); Edmonds et al. (2002) confirm the close connection between carrier transport properties and ferromagnetism in DMS materials showing that typically $`T_c`$ values are the highest in GaMnAs samples with nominally highest conductivities (and presumably the highest hole densities). It has therefore been suggested that, in agreement with the mean-field theory (MFT) for DMS ferromagnetism originally derived in Refs. Abrikosov and Gorkov, 1963; Pashitskii and Ryabchenko, 1979 in a different context and recently rediscovered in Refs. Dietl et al., 2000; Jungwirth et al., 1999, $`T_c`$ in GaMnAs grows monotonically as $`T_cn_\text{c}^{1/3}`$ when the carrier density increases for a fixed Mn concentration. This simple Weiss MFT Abrikosov and Gorkov (1963); Pashitskii and Ryabchenko (1979); Dietl et al. (2000); Jungwirth et al. (1999); Dietl et al. (2001) then implies a convenient technique for enhancing the ferromagnetic transition temperature in GaMnAs, namely, to increase the hole density as much as possible. The general validity of this Weiss MFT-based assertion remains questionable, and it has been arguedChattopadhyay et al. (2001); Hwang et al. (2002) that this prediction holds only in perturbative regime of small $`J`$ and small $`n_\text{c}`$.

The GaMnAs annealing studies bring up important and interesting questions regarding the nature and role of metastable defects in the system that are presumably being healed during annealing leading to $`T_c`$ enhancement. Two different kinds of GaMnAs lattice (atomistic) defects have been discussed in this context. First, there are As antisite (As$`_{\text{Ga}}`$) defects, As atoms sitting at Ga sites, that are invariably present in the low temperature MBE growth required for DMS GaMnAs. These As antisite defects act as double donors with each As defect capturing two holes in GaMnAs. The second type of defects that has been much discussed recently, is the Mn interstitial defect, where the “defective” Mn atom sits at an interstitial site in the GaAs lattice instead of occupying a substitutional cation site replacing a Ga atom. The Mn interstitials are thought to be particularly deleterious in affecting the magnetic properties of GaMnAs because they have two adverse effects: first, they act as donors (similar to As antisite defects) capturing holes; second, the Mn interstitials typically have strong local direct antiferromagnetic coupling to any neighboring substitutional Mn atoms, thereby suppressing the net effective Mn magnetic moment available for DMS ferromagnetism. The quantitative abundance of As antisites and Mn interstitials in GaMnAs is difficult to estimate because there is really no direct experimental technique to observe these defects. It is, however, widely believed that the low-temperature MBE technique, crucial for the homogeneous single-phase growth of GaMnAs, invariably generates both of these defects with their relative importance varying from sample to sample depending on the uncontrollable details of growth and processing. In addition to the atomistic As antisite and interstitial defects in GaMnAs, there are invariably many other unintentional (as well as unknown and uncontrolled) defects and impurities (both charged and neutral) in GaMnAs because low temperature MBE, in general, produces materials of rather poor quality. This poor quality of GaMnAs is reflected in the transport properties as even the best GaMnAs samples seem to have very low carrier mobilities. The measured hole mobilities in the so-called “metallic” GaMnAs systems are only about $`150`$ cm2/V$``$s corresponding to a typical carrier mean free path of $`0.11`$ nm. Such small values of mean free paths would indicate a strong tendency toward carrier localization in GaMnAs, and indeed there are reports of reentrant metal-insulator transitions in GaMnAs as a function of the Mn content $`x`$. Specifically, it has been reportedMatsukura et al. (1998) that Ga1-xMnxAs is an insulator for small ($`x<3\%`$) and large ($`x>7\%`$) values of $`x`$ whereas it is metallic (albeit with very small mean free paths) in the intermediate range of $`x`$ ($`5\%`$) where the ferromagnetic transition temperature is maximized. Other experimental studies (often using careful sample annealing procedures) do not find such reentrant metal-insulator transition behavior.Potashnik et al. (2001); Edmonds et al. (2002)

It is important to emphasize that the existence of DMS ferromagnetism seems to be independent of the system being metallic or insulating. For GaMnAs, both metallic and insulating samples are ferromagnetic with the transition temperature typically being higher for metallic systems although this may not necessarily be a generic behavior. Many other systems exhibiting DMS ferromagnetism, e.g., InMnAs, GeMn, GaMnSb, GaMnN, are however strongly insulating, and as such, metallicity (i.e. itinerant nature of the carriers), is not a necessary pre-condition for the existence of ferromagnetism in DMS systems. Additionally, in Ga1-xMnxAs samples exhibiting reentrant metal-insulator transitions the ferromagnetic behavior appears to be completely continuous as a function of $`x`$ with the only observable effect being a variation in $`T_c`$, which is expected since different GaMnAs samples, even with nominally the same value of $`x`$, show wide variations in $`T_c`$ values. The real DMS carriers mediating the ferromagnetic interaction between the local moments are generically likely to be far from free holes in the valence band of the host semiconductor material. They are, in all likelihood, extended or bound carriers in the impurity (or the defect) band which forms in the presence of the Mn dopants. There is a great deal of direct experimental support for the relevance of this impurity band picture for DMS ferromagnetism, and first principles band structure calculations also confirm the impurity band nature of the carriers active in DMS ferromagnetism. Both the impurity band nature of the carrier system and the presence of strong charge and spin disorder in the system (due to the random Mn dopants as well as other defects, disorder, and impurities invariably present in the DMS material) make carrier localization a relevant issue in DMS ferromagnetism. We believe that understanding the correlation between transport and magnetic properties is a key ingredient in DMS physics.

In the next section of this review we critically discuss some of the proposed theoretical models (and their validity or applicability) for DMS ferromagnetism emphasizing the connection between magnetization (as well as the Curie temperature) and transport properties. We conclude in section III with a brief discussion of (many) open questions and some possible future directions in the subject.

This article is is more of a theoretical perspective; it is not meant to be an exhaustive review of the vast literature on ferromagnetic semiconductors. We only discuss some of the key developments in the subject in order to highlight the physical mechanisms and the important system parameters controlling ferromagnetism in diluted magnetic semiconductors.

## II Theories

The fact that the DMS are ferromagnetic independent of their weakly metallic or strongly insulating nature implies a robust character for the underlying mechanism leading to the long range magnetic order in these systems. Clearly the ferromagnetic mechanism should not depend crucially on the carrier system being “free” valence band holes since the strongly insulating DMS systems do not have any free holes. The currently accepted picture for DMS ferromagnetism is that it is the local antiferromagnetic coupling between the carriers (i.e., holes in GaMnAs) and the Mn magnetic moments that leads to long range ferromagnetic ordering of Mn local moments. The carrier system also becomes spin-polarized in the process with the carrier magnetic moment directed against the Mn magnetic ordering by virtue of the antiferromagnetic hole-Mn coupling, but the total magnetic moment of the spin polarized carriers is extremely small since $`n_\text{c}n_\text{i}`$ and $`|𝐒|>|𝐬|`$ where $`𝐒`$ and $`𝐬`$ are respectively the Mn and the hole spin. The relevant DMS effective magnetic Hamiltonian can be written as

$$H_M=d^3rJ(𝐫)𝐒(𝐫)𝐬(𝐫),$$
(1)
where $`𝐒(𝐫)`$ and $`𝐬(𝐫)`$ are respectively the Mn and hole spin densities. The coupling $`J(𝐫)`$ between Mn local moments and hole spins can, in principle, be ferromagnetic ($`J<0`$) or antiferromagnetic ($`J>0`$), but the effective interaction between the Mn local moments mediated by the holes (through $`H_M`$) is always ferromagnetic. The magnitude of $`J`$ must come from a first principles band structure calculation or from experiments.

Since the Mn moments are localized at specific lattice sites, it is sensible to write Eq. (1) in the more conventional form

$$H_M=J\underset{i}{}d^3r\delta (𝐫𝐑_i)𝐒_i𝐬(𝐫),$$
(2)
where the sum over $`i`$ goes over the Mn sites in the GaAs lattice, and we have assumed the exchange coupling $`J`$ to be a constant. The $`J𝐒_i𝐬`$ local exchange coupling defined in Eq. (2) is sometimes referred to as the Zener model (or the $`sd`$ coupling although in the context GaMnAs, where the carriers are holes, the coupling is more like an $`pd`$ exchange coupling between Mn $`d`$ levels and the $`p`$ valence band).

The magnetic Hamiltonian defined in Eqs. (1) and (2) is, of course, one of the most well-known interaction Hamiltonians in all of condensed matter physics. Depending on the relative magnitudes of hole and Mn moment densities $`n_\text{c}`$ and $`n_\text{i}`$, and the coupling strength $`J`$, $`H_M`$ describes the Kondo model or the Kondo lattice model or $`sf`$ (or $`sd`$) Zener model or the double exchange model or the RKKY model or (in the presence of strong disorder) the (RKKY) spin glass model. Most of the earlier studies of this exchange Hamiltonian have concentrated on the low impurity-density limit, $`n_\text{i}n_\text{c}`$, where the local moments are a perturbation on the carrier Fermi surface. The DMS systems provide an interesting novel regime for studying $`H_M`$, namely the regime of low carrier density $`n_\text{i}n_\text{c}`$. There has not been much earlier work focused on the low carrier-density limit of the Kondo lattice Hamiltonian or the RKKY spin glass Hamiltonian, which is the appropriate parameter regime for GaMnAs. We emphasize that Kondo physics plays no essential role in DMS systems, but because of the strong inherent disorder in these systems spin glass physics may very well be playing a role at lower values of $`n_\text{i}/n_\text{c}`$.

The simplest way to understand DMS ferromagnetism on a qualitative level is to neglect all disorder effects, and assume that the system can be thought of as a collection of local moments of density $`n_\text{i}`$ interacting with itinerant holes of density $`n_\text{c}`$. In the weak coupling regime ($`Jt,E_F`$ where $`t`$ and $`E_F`$ are the band width and the Fermi energy of the carrier system) it is then possible to “eliminate” the carrier degrees of freedom by mapping the problem into the corresponding RKKY problem of Mn local moments interacting indirectly via the holes through $`H_M`$. This carrier-polarization-mediated RKKY exchange interaction is essentially a second order perturbation theoretic calculation in $`J`$, leading to the following interaction Hamiltonian between the Mn spins (assuming, for the sake of simplicity, a single parabolic hole band)

$$H_i=\underset{ij}{}J_{ij}𝐒_i𝐒_j,$$
(3)
with

$$J_{ij}|J|^2\left[\frac{\mathrm{sin}(2k_FR)(2k_FR)\mathrm{cos}(2k_FR)}{(2k_FR)^4}\right],$$
(4)
where $`k_Fn_\text{c}^{1/3}E_F^{1/2}`$ is the Fermi wave vector for the holes and $`R|𝐑_{ij}||𝐑_i𝐑_j|`$ is the distance between the Mn impurities at $`i`$ and $`j`$ lattice sites. This oscillatory RKKY indirect exchange magnetic coupling between local moments placed in an electron gas arises from the spin polarization induced in the electron system by the local moment, and is a perturbative effect of the local moments on the carrier system (valid in the limit of small $`J`$). In the DMS systems an approximate average distance between the Mn local moments is $`\overline{R}n_\text{i}^{1/3}`$, making typical values of $`k_FR(n_\text{c}/n_\text{i})^{1/3}`$. For ferromagnetism to occur (remembering that the real GaMnAs system is intrinsically strongly substitutionally disordered) one must avoid the strong frustration effects associated with random sign changes in the magnetic interaction of Eq. (3) arising from the oscillatory terms in Eq. (4), which can only be guaranteed when $`k_FR1`$. This then necessitates the condition $`n_\text{c}/n_\text{i}1`$, making strong compensation, i.e., $`n_\text{c}n_\text{i}`$, a necessary condition for ferromagnetism in the system.

We note that a Weiss MFT calculation can easily be carried out for the coupled Mn-hole magnetic problem defined by the Zener-RKKY model of Eqs. (1)-(4). For a simple single-band degenerate hole model, the result for $`T_c^{\text{MF}}`$ in the Weiss MFT was obtained a very long time ago:Abrikosov and Gorkov (1963); Pashitskii and Ryabchenko (1979)

$$T_c^{\text{MF}}=\frac{S(S+1)}{3}s^2|J|^2D(E_F)n_\text{i},$$
(5)
where $`S`$ is the local moment spin and $`s`$ is the carrier spin. The carrier density of states $`D(E_F)`$ in Eq. (5), in the degenerate one band free carrier system, is given by $`D(E_F)E_F^{1/2}n_\text{c}^{1/3}`$. Thus $`T_c^{\text{MF}}`$ increases monotonically with the exchange coupling, the local moment density, and the carrier density as

$$T_c^{\text{MF}}J^2n_\text{c}^{1/3}n_\text{i},$$
(6)
where $`n_\text{c}`$ and $`n_\text{i}`$ are treated as independent density parameters. Based on this simple Weiss MFT (and its various extensions incorporating spin wave corrections and/or explicit spin-orbit coupling effects in the GaAs valence band), quantitative predictions have been madeDietl et al. (2001) about the dependence of the ferromagnetic transition temperature in various DMS systems on the system parameters (carrier and local moment densities, effective exchange coupling strength, etc.). In addition, we have recently shownDas Sarma et al. (2003) that the MFT for the model defined by Eqs. (1) and (2) can be extended to the nondegenerate carrier system more appropriate for the localized holes in the strongly insulating DMS materials. In contrast to the degenerate results of Eq. (6), which is appropriate for the metallic (“extended”) carrier system (e.g. free valence band holes), the nondegenerate MFT provides a transition temperature dependence given by

$$T_c^{\text{MF}}|J|(n_\text{c}n_\text{i})^{1/2}.$$
(7)
Thus, the dependence of $`T_c^{\text{MF}}`$ on the system parameters changes drastically in the localized nondegenerate limit. More details can be found in Ref. Das Sarma et al., 2003.

The simple Weiss mean-field theory (Eqs. (5) and (6)) based on the model of degenerate valence band holes interacting with the Mn local moments (and its obvious extensions) has been used extensively in the literature. The question, therefore, arises about its validity, or more generally, about its quantitative reliability. It is argued that the molecular MFT should apply well in DMS systems because of the large length scales (e.g. $`k_F^1`$) involved in the problem. We believe that there are good reasons to question the validity of the Weiss MFT as applied to DMS ferromagnetism. First, strong disorder in the system invariably brings in some effects of frustration which should become more significant at larger values of carrier density, making the simple MFT defined by Eqs. (5) and (6) increasingly incorrect at higher carrier densities (even for the metallic system). In fact, $`T_c`$ should vanish in the disordered system as $`n_\text{c}n_\text{i}`$. Second, MFT in this problem being equivalent to a second order perturbation theory in the exchange coupling $`J`$ (i.e. Eqs. (1)–(6)), the validity of Weiss mean-field predictions becomes highly questionable for large values of $`J`$ where carriers may bind to individual local moment sites to lower their energy forming an impurity band. There is significant experimental evidence for impurity band formation in DMS materials, which is not included in the MFT. Therefore mean-field predictions will fail at larger values of $`J`$ where DMS magnetic properties should be dominated by impurity band physics not caught by Eqs. (5) and (6). We have recently developed a dynamical mean-field theory (DMFT) pictureChattopadhyay et al. (2001); Hwang et al. (2002) of DMS ferromagnetism where impurity band physics is explicitly included. Third, in the limit of $`n_\text{i}n_\text{c}`$, where DMS ferromagnetism prevails, disorder effects are extremely strong (as is obvious from the insulating nature of most DMS materials and from the extremely low mobilities of the so-called “metallic” DMS materials which may very well also be insulating at $`T=0`$), and therefore the degenerate “metallic” Weiss MFT approach based on the carriers being the free extended valence band holes of the host semiconductor may be fundamentally flawed. A more appropriate picture in this disordered localized regime may be the percolation picture of DMS ferromagnetism recently developed by usKaminski and Das Sarma (2002) where each hole is bound in a cluster of magnetic impurities forming a bound magnetic polaron. With decreasing temperature, these bound magnetic polarons coalesce eventually leading to a magnetic percolation transition at $`T_c`$ where a magnetic percolation cluster spans the whole system. This polaron percolation picture of DMS ferromagnetism is strongly supportedAlvarez and Dagotto (2002) by direct numerical simulations and by experimental studies showing strongly concave magnetization curves in many DMS systems which follow naturally from our theory.Das Sarma et al. (2003); Kaminski and Das Sarma (2002)

Below we provide some details on the dynamical mean-field and polaron percolation theories of DMS ferromagnetism.

### II.1 Dynamical mean-field theory

In this section we briefly describe the “dynamical mean-field theory” (DMFT). Due to size limitations, we are not able to give detailed description of this formalism here. A reader interested in more details may find them in Ref. Chattopadhyay et al., 2001; Hwang et al., 2002; Das Sarma et al., 2003.

We model the Ga1-xMnxAs system as a lattice of sites, which are randomly nonmagnetic (with probability $`1x`$) or magnetic (with probability $`x`$), where $`x`$ now indicates the relative concentration (i.e. per Ga site) of active Mn local moments in Ga1-xMnxAs. The DMFT approximation amounts to assuming that the self energy is local or momentum independent, $`\mathrm{\Sigma }(𝐩,i\omega _n)\mathrm{\Sigma }(i\omega _n)`$, and then all of the relevant physics may be determined from the local (momentum-integrated) Green function defined by

$$G_{\text{loc}}(i\omega _n)=a_0^3\frac{d^3p}{(2\pi )^3}\frac{1}{i\omega _n+\mu ϵ(p)\mathrm{\Sigma }_\sigma (i\omega _n)},$$
(8)
where we have normalized the momentum integral to the volume of the unit cell $`a_0^3`$, and $`\mu `$ is the chemical potential. $`G_{\text{loc}}`$ is in general a matrix in spin and band indices and depends on whether one is considering a magnetic or non-magnetic site. Since $`G_{\text{loc}}`$ is a local function, it is the solution of a local problem specified by a mean-field function $`g_0`$, which is related to the partition function $`Z_{\text{loc}}=𝑑\text{S}\mathrm{exp}(S_{\text{loc}})`$ with action

$`S_{\text{loc}}`$ $`=`$ $`{\displaystyle \underset{\alpha \beta }{}}g_{0\alpha \beta }^a(\tau \tau ^{})c_\alpha ^{}(\tau )c_\beta ^{}(\tau ^{})`$ (9)
$`+`$ $`J{\displaystyle \underset{\alpha \beta }{}}\left(\text{S}𝝈_{\alpha \beta }\right)c_\alpha ^{}(\tau )c_\beta ^{}(\tau ^{}),`$
on a magnetic site and

$$S_{\text{loc}}=\underset{\alpha \beta }{}g_{0\alpha \beta }^b(\tau \tau ^{})c_\alpha ^{}(\tau )c_\beta ^{}(\tau ^{}),$$
(10)
on a non-magnetic site. Here $`c_\alpha ^{}(\tau )`$ ($`c_\alpha ^{}(\tau )`$) is the destruction (creation) operator of a fermion in the spin state $`\alpha `$ and at time $`\tau `$. $`g_0(\tau \tau ^{})`$ plays the role of the Weiss mean field (bare Green function for the local effective action $`S_{\text{loc}}`$) and is a function of time. The magnetic-site mean-field function $`g_0^a`$ can be written as $`g_{0\alpha \beta }^a=a_0+a_1\text{m}𝝈_{\alpha \beta }`$ with m the magnetization direction and $`a_1`$ vanishing in the paramagnetic state ($`T>T_c`$). Since the spin axis is chosen parallel to m, $`g_0^a`$ becomes a diagonal matrix with components parallel ($`g_0^a=a_0+a_1`$) and antiparallel ($`g_0^a=a_0a_1`$) to m. It is specified by the condition that the local Green function computed from $`Z_{\text{loc}}`$, namely $`\delta \mathrm{ln}Z_{\text{loc}}/\delta g_0^a=\left(g_0^a\mathrm{\Sigma }\right)^1`$ is identical to the local Green function computed by performing the momentum integral using the same self energy.

Within this approximation we calculate the normalized magnetization of the local moments with the semicircle density of states, $`D(\omega )=\sqrt{4t^2\omega ^2}/2\pi t`$, where $`t`$ is a bandwidth of the system. The normalized magnetization $`M(T)`$ is given by $`M(T)=(d𝐒)\widehat{𝐒}\mathrm{exp}(S_{\text{loc}})/Z_{\text{loc}}`$. As the temperature is increased, the spins disorder and eventually the magnetic transition temperature is reached. Above this temperature, $`g_0`$ is spin-independent. By linearizing the equation in the magnetic part of $`g_0`$ with respect to $`a_1`$ we may obtain the ferromagnetic transition temperature $`T_c`$. The details on the calculation of $`T_c`$ are given in Refs. Chattopadhyay et al., 2001; Hwang et al., 2002. In Fig. 1 we show the calculated $`T_c`$ as a function of carrier density for $`x=0.05`$ and various couplings $`J`$, and the corresponding density of states are given in the inset. When $`J<t`$ the impurity band formation dose not occur (see the inset for $`J=0.5t`$) and $`T_c`$ are saturated as the density increases. However, as $`J>t`$ the impurity spin bands are well established (see the inset for $`J=2.0t`$). In this limit the $`T_c`$ has a maximum value around the half filling of the impurity band ($`n_c0.5x`$) and $`T_c`$ vanishes as the carriers fill the band ($`n_c=x`$) because no low energy hopping processes are allowed in a ferromagnetic state for a filled impurity band. Within DMFT the calculated $`T_c`$ shows the nonmomotonic behavior for all $`J`$ and the Weiss mean field prediction $`T_cn^{1/3}`$ can be applied only for small $`n_c`$.

In Fig. 2 we show the normalized magnetization of the local moments as a function of temperature for different values of $`J=`$1.0, 1.5, 2.0$`t`$ and $`x=0.05`$, and for various hole densities, $`n_\text{c}/n_\text{i}`$. For the small coupling constant $`J=t`$ the impurity band is not formed, but for $`J=`$1.5, 2.0$`t`$ we have a spin polarized impurity band. For relatively high density ($`n_\text{c}/n_\text{i}=0.4`$) the calculated magnetization looks similar to the Weiss mean-field results. But for low density ($`n_\text{c}/n_\text{i}=0.04`$) we have a linear $`M(T)`$ in the intermediate temperature range. Near the critical temperature $`T_c`$ the critical behavior of the magnetization for all density is given by $`M(T)(T_cT)^{1/2}`$. For different exchange couplings we have similar results (*i. e.*, linear behavior at low densities and intermediate temperature ranges).

In particular, it should be possible to obtain the $`M(T)`$ behavior for the localized carrier case also from DMFT by incorporating impurity band localization in the DMFT formalism. Our current theory does not include localization, and the impurity band (or valence band) carriers in our DMFT calculations are all delocalized metallic carriers. First principles band theory calculations indicate that the actual exchange coupling in Ga1-xMnxAs may be close to critical $`J_c`$, and as such impurity band physics may be quite important for understanding DMS magnetization. To incorporate physics of localization one needs to include disorder effects (invariably present in real DMS systems) in the model. All our DMFT calculations are done in the virtual crystal approximation where effective field is averaged appropriately leaving out random disorder effects explicitly. In the next section we explicitly incorporate disorder in the theory by developing a percolation theory approach to DMS magnetization for the strongly localized insulating systems.

### II.2 Percolation theory

Our percolation theory for DMSKaminski and Das Sarma (2002) applies strictly in the regime of strongly localized holes where the dynamical mean-field theory for delocalized carriers described above has little validity. These two theories, mean-field theory and percolation theory, are therefore complementary.

The percolation theory assumes the same model of carrier-mediated ferromagnetism, but now the carriers are pinned down with the localization radius $`a_B`$. The disorder, averaged out in the mean-field theory, plays a key role in the carrier localization. The magnetic impurities are assumed to be completely randomly distributed in the host semiconductor lattice in contrast to the mean-field case where the carrier states are free and the disorder is neglected.

As we have demonstrated in Ref. Kaminski and Das Sarma, 2002, the problem of ferromagnetic transition in a system of bound magnetic polarons can be mapped onto the problem of overlapping spheres well-known in the percolation theory.Shklovskii and Efros (2001) The latter problem studies spheres of the same radius $`r`$ randomly placed in space (three-dimensional in our case) with some concentration $`n`$. Overlapping spheres make “clusters;” as the sphere radius $`r`$ becomes larger, more and more spheres join into clusters, the clusters coalesce, and finally, at some critical value of the sphere radius, an infinite cluster spanning the whole sample appears. This problem has only one dimensionless parameter, $`r^3n`$, and therefore can be easily studied by means of Monte-Carlo simulations.

Each sphere of the overlapping spheres problem corresponds to a bound magnetic polaron, which is a complex formed by one localized hole and many magnetic impurities with their spins polarized by the exchange interaction with the hole spin. The concentration $`n`$ of spheres coincides with the concentration $`n_\text{c}`$ of localized holes. The expression for the effective polaron radius in terms of the physical parameters of the system under consideration is not trivial and has been found in our earlier work:Kaminski and Das Sarma (2002)

$$r^3n=\left[0.86+\left(a_B^3n_\text{c}\right)^{\frac{1}{3}}\mathrm{ln}\frac{T_c}{T}\right]^3.$$
(11)
Here $`0.640.86^3`$ is the critical value of the parameter $`r^3n`$ at which the infinite cluster appears, and $`T_c`$ is the Curie temperature of the ferromagnetic system under consideration, derived in Ref. Kaminski and Das Sarma, 2002,

$$T_csSJ\left(\frac{a_0}{a_B}\right)^3\left(a_B^3n_\text{c}\right)^{\frac{1}{3}}\sqrt{\frac{n_\text{i}}{n_\text{c}}}\mathrm{exp}\left(\frac{0.86}{\left(a_B^3n_\text{c}\right)^{\frac{1}{3}}}\right).$$
(12)
The limit of applicability of Eq. (12) is determined by the condition $`a_B^3n_\text{c}1`$. The dependence of $`T_c`$ on $`a_B^3n_\text{c}`$ is shown in Fig. 3.

Since $`n_\text{c}n_\text{i}`$, one polaron includes many magnetic impurities, and the total magnetization of the sample is that of impurities:

$$\frac{M(T)}{M_0}=𝒱\left(0.86+\left(a_B^3n_\text{c}\right)^{\frac{1}{3}}\mathrm{ln}\frac{T_c}{T}\right),$$
(13)
where the universal function $`𝒱(y)`$ is the infinite cluster’s volume in the model of overlapping spheres; it depends only on the product $`y`$ of the spheres’ diameter and the cubic root of their concentration. One can see that the shape of the magnetization curve is determined by only one dimensionless parameter $`a_B^3n_\text{c}`$, while the expression (12) for $`T_c`$ is more complicated and depends on all parameters of the model. Fig. 4 shows the temperature dependence of the magnetization at two values of $`a_B^3n_\text{c}`$; the curve is more concave at smaller values of this parameter. The concave shape of the curve is consistent with the experimental magnetization data in Ge1-xMnxPark et al. (2002) and low-$`T_c`$ III-V samplesOhno et al. (1992); Chen et al. (2002) where our polaron percolation picture applies better due to stronger carrier localization associated with lower values of $`a_B^3n_\text{c}`$. Our magnetization results also agree with the numerical results of Ref. Berciu and Bhatt, 2001; Alvarez and Dagotto, 2002. Very recently, a direct numerical Hartree-Fock calculation has convincingly verified the magnetic polaron percolation picture for the localized regime.Yang and MacDonald (2003)

## III Conclusion

When carriers are present with a carrier density $`n_c`$ in a semiconductor containing a certain magnetic impurity density $`n_\text{i}`$ of local magnetic moments, a Weiss mean field theory, developed years ago,Abrikosov and Gorkov (1963); Pashitskii and Ryabchenko (1979) within the Zener-RKKY effective magnetic Hamiltonian describing the local exchange coupling between local moments and carrier spin, would always predict ferromagnetism with a mean field transition temperature $`T_c^{\text{MF}}`$ varying linearly in $`n_\text{i}`$ and $`n_c^{1/3}`$. This Weiss mean field theory, appropriately modified by the complicated spin-orbit coupled multiband valence band structure of GaAs, has been extensively used in making quantitative predictions about the magnetic properties of GaMnAs. This Weiss mean field theory, while being a powerful qualitative tool, is obviously too simplistic to be taken seriously for quantitative analyses of DMS properties. In real DMS systems spatial fluctuations (i.e. disorder associated with random positions of the magnetic dopants) and thermal fluctuations of magnetic moments as well as impurity band and discrete lattice effects (all neglected in the Weiss mean field theory) are likely to be of real importance even if the magnetic coupling can be assumed to be a simple local exchange coupling between local impurity moments and carrier spins. In addition, the mean field theory averages out the oscillatory exchange coupling between the impurity moments, which must be important at higher carrier densities, particularly in the presence of strong spatial disorder. For example, the mean field theory incorrectly predicts the ground state to be ferromagnetic for *all* values of $`n_c`$ and $`n_\text{i}`$, whereas in reality of course the system is a spin glass for larger values of $`n_c`$. The mean field theory is qualitatively valid only for very small values of the carrier-local-moment exchange coupling $`J`$ where impurity band effects are weak, and applies only in the limit of $`n_cn_\text{i}`$ where disorder and oscillatory aspects of exchange can be neglected. In addition, the standard mean field theory is valid only for degenerate metallic systems although a nondegenerate localized version of the mean field theory has recently been developed.

There have been recent theoretical developmentsChattopadhyay et al. (2001); Hwang et al. (2002); Kaminski and Das Sarma (2002); Das Sarma et al. (2003) going beyond the simple Weiss mean field theory where impurity band effects (both for metallicChattopadhyay et al. (2001); Hwang et al. (2002) and insulatingKaminski and Das Sarma (2002) DMS systems) are explicitly included in the dynamical mean fieldChattopadhyay et al. (2001); Hwang et al. (2002); Das Sarma et al. (2003) and magnetic polaron percolation theoriesKaminski and Das Sarma (2002); Das Sarma et al. (2003). The DMFT theory predicts, in contradiction with the Weiss mean field theory, that the ferromagnetic transition temperature $`T_c`$ is not monotonic in the carrier density (and the coupling strength $`J`$), and may vanish for larger values of $`n_c`$. While the definitive quantitative theory for DMS ferromagnetism, taking into account complete band structure complications of the system along with disorder, fluctuation, and nonperturbative strong-coupling (i.e. $`J`$ not necessarily small) effects in a consistent manner is still lacking, it is increasingly clear that disorder and impurity band aspects of the real DMS systems are extremely important in understanding DMS magnetic properties, and theories Chattopadhyay et al. (2001); Hwang et al. (2002); Kaminski and Das Sarma (2002); Das Sarma et al. (2003) that include these effects should be of qualitative and quantitative significance in explaining DMS magnetic properties.

The observed correlation between transport and magnetic properties in DMS systems, e.g. the more metallic systems typically having more convex magnetization curves as a function of temperature whereas more insulating systems having extreme non-mean-field like concave magnetization versus temperature curves (with considerable missing magnetic moments), is perhaps a strong indicator of the underlying mechanism of DMS ferromagnetism.Das Sarma et al. (2003) This correlation indicates a carrier-mediated magnetic interaction origin of DMS ferromagnetism. In particular, two very recent theoretical publicationsDas Sarma et al. (2003); Yang and MacDonald (2003) have discussed in considerable details this correlation between metallicity and DMS ferromagnetism. In Ref. Das Sarma et al., 2003 it has been argued that the appropriate picture for DMS ferromagnetism in strongly disordered insulating materials is the bound magnetic polaron percolation picture whereas at higher densities (and/or lower disorder), where the system is metallic, the dynamical mean-field picture (which becomes equivalent to the Weiss mean field picture at low values of exchange coupling insufficient to cause the impurity band formation) is more appropriate. In Ref. Yang and MacDonald, 2003 a detailed numerical simulation of the disordered DMS model has been carried out qualitatively validating this picture. The question therefore arises regarding the nature of the DMS ground state: Is it localized and insulating or extended and metallic or is there a transition between the two as a function of carrier density? If there is a true metal-insulator transition, then the percolation picture holds in the insulating phase and the dynamical mean field picture holds in the metallic phase. Although there have been experimental claims of metal-insulator transitions in GaMnAs systems as a function of Mn content, the current experimental situation is sufficiently murky that is possible that all GaMnAs systems are in fact insulating at $`T=0`$ for all values of the Mn content. It would therefore be desirable to develop a dynamical mean field theory (or even just the Weiss mean field theory) of DMS ferromagnetism explicitly incorporating disorder effects so that the magnetic properties can be studied continuously through the metal-insulator transition (or crossover, as the case may be).

This work is supported by US-ONR and DARPA.