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# CNO Line Radiation and the X-ray Bowen Fluorescence Mechanism in Optically-Thick, Highly-Ionized Media

## 1 Introduction

Radiative transfer effects are capable of producing line spectra that differ substantially from those emitted under optically thin conditions. As resonance line photons travel through a medium that is optically thick to its own radiation, multiple non-coherent scattering substantially alters the line profiles of the emergent spectrum. Line transfer also affects the emergent line intensities through line or continuum absorption, in which case the energy is either (1) re-radiated through other discrete transitions or (2) is used in heating the ambient gas. In hydrogen-like ions, for example, the upper levels of the higher-series Lyman transitions ($`\beta `$, $`\gamma `$, $`\delta `$, etc.) have finite probabilities of decaying to excited states. This implies that the Lyman line photons will be destroyed and re-radiated in the Balmer, Paschen, etc. series if the line optical depths are sufficiently large. Ratios of Lyman to Balmer line intensities, for example, can then be used to estimate the optical depth, as well as other local physical parameters, such as the density and temperature (see, e.g., Drake & Ulrich 1980, and references therein).

Another well-known example of such an effect is the Bowen fluorescence mechanism (Bowen, 1934, 1935), where it was realized that the coincidence in the wavelengths of He II (He+) Ly$`\alpha `$ and O III (O2+) $`2p`$$`3d`$ transitions allows the conversion of He II Ly$`\alpha `$ line photons into the upper levels of O III, which then decay to produce lines in the optical/UV band known as the Bowen lines at $`\lambda 30004000`$ Å. These line were commonly found to be extraordinarily strong in the optical spectra of planetary nebulae and Seyfert galaxies. Unno (1955) presented the first complete analysis of the He II Ly$`\alpha `$ transfer and the conversion efficiencies of the Bowen lines, and demonstrated that the observed spectral properties can be reasonably well-described by this mechanism. Subsequently, Weymann & Williams (1969) presented a more detailed calculation using an exact form of the redistribution function and a realistic ionization balance calculation (see, also, Harrington 1972; Kallman & McCray 1980; Eastman & MacAlpine 1985; Netzer, Elitzur, & Ferland 1985).

In the simplest approximation generally adopted for spectral modeling, one assumes that line photons created in the gas escape the medium without any further interaction with the constituent atoms in the medium. This is generally referred to as the optically-thin limit or the coronal approximation in the context of collisionally ionized plasma. In this limit, the ionization balance is determined solely by the local temperature and is assumed to be entirely decoupled from the radiation field. The emission spectra computed under these assumptions seem to apply fairly well to the observed X-ray spectra of a wide variety of sources including stellar coronae, supernova remnants, hot diffuse gas in starburst galaxies, and the intergalactic medium in clusters of galaxies.

For photoionized plasmas, on the other hand, codes such as Cloudy (Ferland et al., 1998) and XSTAR (Kallman & McCray, 1982; Bautista & Kallman, 2001) treat the transfer of X-ray lines using either the escape probability method or the assumption of complete redistribution. While these assumptions yield reasonable results for isolated lines with moderate line optical depths ($`\tau 10`$), it does not properly describe line scattering when absorption in the damping wings becomes important (i.e., for $`\tau 1001000`$ depending on the Voigt parameter; see, e.g., Shine, Milkey, & Mihalas 1975). Such conditions might be relevant for a wide variety of astrophysical environment including ionized surface layers of accretion disks, extended circumsource regions in AGN, and possibly shocked regions in the stellar wind of hot young stars.

The purpose of this paper is to demonstrate that radiative transfer effects can alter intensities of some of the brightest emission lines in the X-ray band, in particular, the hydrogen- and helium-like lines from carbon, nitrogen, and oxygen. Non-solar CNO abundance ratios have been inferred in a number of sources observed with the grating spectrometers on Chandra and XMM-Newton. The relativistic emission line interpretation of the XMM-Newton RGS spectra of the Seyfert 1 galaxies MCG$``$6-30-15 and Mrk 766 presented by Branduardi-Raymont et al. (2001), for example, requires the nitrogen emission lines, which are presumably formed in an optically thick accretion disk, to be much stronger than that of the oxygen line assuming solar abundance ratios (see also, Mason et al. 2003). Similarly, Kinkhabwala et al. (2002) conclude that nitrogen in the extended circumnuclear regions in the Seyfert 2 galaxy NGC 1068 is overabundant by a factor of $`3`$ based on measurements of the hydrogen- and helium-like line intensities with the RGS (see also, Brinkman et al. 2002; Ogle et al. 2003). Jimenez-Garate et al. (2002) also report abnormally high nitrogen line intensities relative to those of oxygen in the RGS spectrum of the low-mass X-ray binary Her X-1, and interpreted as an overabundance of nitrogen due to H-burning by the CNO-cycle. All of the modeling, however, are based on rather simple models that do not include detailed line transfer. We show that the effects of line overlap alone can explain some of the observed anomalies, in particular the strength of the nitrogen lines, if the optical depth is large, and that detailed transfer models are required to infer accurate values for the CNO abundances with X-ray spectroscopic data. We note, however, that the theoretical model presented here is highly idealized in order to simply illustrate the general effects and describe the relevant spectroscopic details, and is certainly not adequate for quantitative comparisons with observations of complicated systems.

The paper is organized as follows. In §2, we describe the spectroscopic properties of the frequency range near the O VIII (O7+) Ly$`\alpha `$ doublet transitions, which contains a pair of overlapping N VII (N6+) Ly$`\zeta `$ lines and underlying sources of continuum opacity, which is usually dominated by K-shell absorption of H- and He-like carbon (C4+ and C5+) and He-like nitrogen (N6+). We compute the destruction probabilities of O VIII Ly$`\alpha `$ due to line absorption by the N VII Ly$`\zeta `$ transition and continuum absorption by carbon and nitrogen for temperatures ranging from cool photoionized media ($`kT10\mathrm{eV}`$) to hot collisionally ionized plasmas ($`kT1\mathrm{keV}`$), which is described in §3. We demonstrate that the wavelength coincidence allows efficient conversion of O VIII Ly$`\alpha `$ line radiation into the N VII lines, and may be misidentified as a CNO abundance anomaly (§4). Finally, in §5, a few other potentially important overlaps are identified and their effects on the global X-ray spectrum under optically thick conditions are briefly discussed.

## 2 Spectroscopy

In the non-relativistic, hydrogenic approximation, the transition energy of the O VIII Ly$`\alpha `$ line ($`n=21`$) coincides exactly with that of the N VII Ly$`\zeta `$ ($`n=71`$) line; i.e., $`Z_a^2(11/n^2)=Z_b^2(11/m^2)`$ holds exactly for $`Z_a=8`$, $`n=2`$ and $`Z_b=7`$, $`m=7`$. More precisely, the O VIII Ly$`\alpha `$ transition is a doublet at wavelengths $`\lambda _{\mathrm{Ly}\alpha _1}=18.96711`$ Å ($`653.680\mathrm{eV}`$) and $`\lambda _{\mathrm{Ly}\alpha _2}=18.97251`$ Å ($`653.494\mathrm{eV}`$) that correspond to decays to the ground state from the $`{}_{}{}^{2}P_{3/2}^{}`$ and $`{}_{}{}^{2}P_{1/2}^{}`$ levels, respectively. The oscillator strength of the Ly$`\alpha _1`$ line is twice that of the Ly$`\alpha _2`$ line. The N VII Ly$`\zeta `$ transition is also a doublet with $`\lambda _{\mathrm{Ly}\zeta _1}=18.97411`$ Å ($`653.439\mathrm{eV}`$) and $`\lambda _{\mathrm{Ly}\zeta _2}=18.97418`$ Å ($`653.436\mathrm{eV}`$). Since the wavelength difference of $`0.07`$ mÅ is much too small to be resolved at any reasonable temperature where N6+ can exist, we simply treat them as a single line with an oscillator-strength-averaged wavelength of $`\lambda =18.97413`$ Å ($`653.438\mathrm{eV}`$; see, Figure 1). The O VIII Ly$`\alpha `$ and N VII Ly$`\zeta `$ transition wavelengths are adopted from Johnson & Soff (1985) and Garcia & Mack (1965), respectively, which include reduced-mass and quantum electrodynamical corrections to the eigenvalues of the Dirac equation111see, also the NIST Atomic Spectra Database – http://physics.nist.gov/cgi-bin/AtData/main\_asd. Oscillator strengths and radiative decay rates are calculated using the Flexible Atomic Code (FAC222ftp://space.mit.edu/pub/mfgu/; Gu 2003). All of the relevant atomic parameters are listed in Table 1.

The relative cross sections assuming solar abundances ($`A_\mathrm{N}/A_\mathrm{O}`$ = 0.13; Anders & Grevesse 1989) and a temperature of $`kT=10\mathrm{eV}`$, typical for a photoionization-dominated medium at this level of ionization, are shown in Figures 2. At this temperature, the N VII Ly$`\zeta `$ lies approximately 2 Doppler widths away from the O VIII Ly$`\alpha _2`$ line and 10 Doppler widths from the Ly$`\alpha _1`$ line. The cross section is almost three orders of magnitude lower than that of the O VIII lines, which implies that significant scattering between the lines occur when the total optical depth is $`10^3`$. Similarly, at a temperature of $`kT=50\mathrm{eV}`$, the N VII Ly$`\zeta `$ lies $`1`$ Doppler width away from the O VIII Ly$`\alpha _2`$ line and 4 Doppler widths from the Ly$`\alpha _1`$ line, as shown in Figure 3.

The emission coefficient in this spectral range is dominated almost entirely by the O VIII Ly$`\alpha `$ lines. The intrinsic N VII Ly$`\zeta `$ emission coefficient is approximately two to three orders of magnitude lower in both collision-dominated and recombination-dominated plasmas with solar $`A_\mathrm{N}/A_\mathrm{O}`$ abundance ratio. If the medium is photoionized by some external source of continuum radiation, photoexcitation may enhance the line emissivities of the N VII lines, but this is important only in the surface layer within $`\tau 10`$, as external radiation will not be able to penetrate deeper into the medium. Since we are primarily interested in the properties of the Bowen mechanism at large optical depths, we ignore the N VII Ly$`\zeta `$ intrinsic source term entirely.

Absorption of an O VIII line photon by N VII is followed by one of the following two processes: (1) re-emission in the N VII Ly$`\zeta `$ line, which results in a pure scattering event or (2) destruction of the line through cascades via the upper levels ($`n=26`$), followed eventually by decay to the ground level. Collisional excitation and de-excitation from these levels are important at only extremely high electron densities ($`n_{\mathrm{e},\mathrm{crit}}10^{21}\mathrm{cm}^3`$), and so we do not consider these processes here. We note, however, that thermalization of the line photons via collisions may occur at sufficiently high density and high optical depth, such that $`n_eN_{\mathrm{line}}n_{\mathrm{e},\mathrm{crit}}`$, where $`N_{\mathrm{line}}`$ is the mean number of scatterings experienced by the line photons as they propagate through the medium.

The branching ratios for the two possible processes can be determined from the radiative decay rates from the $`7p`$ level to all possible levels. We use radiative rates calculated with FAC except for the two-photon decay rates, which are adopted from Drake (1986). The branching ratios for processes (1) and (2) are found to be 0.797 and 0.203, respectively. The final fate of the 20.3% of the line photons that initially decay to an upper level can be understood by computing the cascade matrices; quantities that represent the probabilities of one state decaying to another state via all possible channels (Seaton, 1959). We find, for example, that 58% of them produce the Balmer, Paschen, etc. lines and eventually result in two-photon emission from the $`2{}_{}{}^{2}S_{1/2}^{}`$ level, while the remaining 42% produce the Lyman lines in the soft X-ray band.

Continuum opacity from ions that coexist with O VIII is dominated primarily by C V (ionization potential $`\chi =31.622`$ Å), C VI ($`\chi =25.303`$ Å), and N VI ($`\chi =22.458`$ Å) for both collisionally and photoionized plasmas in ionization and thermal equilibrium. The threshold wavelength of N VII ($`\chi =18.587`$ Å) lies shortward of the O VIII Ly$`\alpha `$ line. Lower charge states of carbon and nitrogen may contibute very small amounts of continuum opacity as well. For solar abundances, the typical value for the combined continuum opacity relative to the O VIII Ly$`\alpha `$ line opacity is $`10^4`$, but can range anywhere from a $`\mathrm{few}\times 10^6`$ to as high as $`10^3`$ depending on the level of ionization and the temperature. In ionization equilibrium, a carbon or nitrogen ion that absorbs the O VIII Ly$`\alpha `$ line will be photoionized, and will eventually recombine to form emission lines and continua. In a recombination-dominated plasma at a temperature of $`kT100\mathrm{eV}`$, for example, calculations show that approximately 50% of the total number of recombinations produce one of the Lyman lines.

Under most circumstances, the Compton cross section is roughly two orders of magnitude below the continuum absorption cross section. This implies that lines photons are preferentially absorbed before they are Compton scattered and, therefore, continuum absorption is the dominant mechanism that competes with the line processes. Compton scattering effects will, however, be important in extremely highly-ionized regions, where only trace abundances of bound ions can survive or in low-metalicity plasmas with abundances $`1`$% solar. These will be ignored entirely in the present work.

## 3 Computational Method

To illustrate the importance of line overlap, we assume an infinite, symmetric slab with a pre-specified source distribution of line photons. In reality, dynamical effects, such as velocity gradients and turbulence, as well as inhomogenieties that exist, for example, in accretion disks complicate the problem, but we ignore them in the present study. Although resonance line scattering, in general, produces polarized light, we assume that the radiation field is unpolarized (cf., Lee, Blandford, & Western 1994). To simpify the computational procedure even further, the medium is assumed to be isothermal with a constant level of ionization. We solve the radiative transfer equation in the frequency range near the O VIII Ly$`\alpha `$ lines by properly accounting for scattering and absorption by the various overlapping lines, as well as the presence of a background continuum opacity source. Using the emergent intensity, we then compute the escape probabilities of the original O VIII Ly$`\alpha `$ line photons and conversion efficiencies into the N VII lines and photoelectric absorption as functions of the total optical depth of the slab.

The radiative transfer equations for rays propagating in the $`+\mu `$ and $`\mu `$ directions ($`\mu cos\theta `$, where $`\theta `$ is the angle from the normal $`z`$-axis) in a plane-parallel medium can be written as,

$$\pm \mu \frac{I(z,\nu ,\pm \mu )}{z}=\underset{i}{}k_i(\nu )[S_i(z,\nu )I(z,\nu ,\pm \mu )]$$
(1)
where $`\theta `$ is the angle measured from the $`z`$-direction, which we define to be normal to the slab. The right-hand-side is summed is over all possible sources of opacity and emissivity in the slab. We express the frequency in terms of the frequency shift from the reference line center at frequency $`\nu _0`$ in units of the Doppler width $`\mathrm{\Delta }\nu _D`$, i.e., $`x=(\nu \nu _0)/\mathrm{\Delta }\nu _D`$, and write the line absorption coefficient (cm-1) as $`k_i(x)=k_{iL}\varphi _a(x)`$.

Since most X-ray resonance lines have large radiative decay rates ($`A_r10^{12}\mathrm{s}^1`$), the population of the upper level is usually negligible compared to that of the ground state. Denoting the transition oscillator strength as $`f_{ul}`$ and the lower-level density as $`n_i`$ ($`\mathrm{cm}^3`$), we can then write,

$$k_{iL}=\frac{\pi e^2}{m_ec}\frac{f_{ul}n_i}{\mathrm{\Delta }\nu _D},$$
(2)
and $`\varphi _a(x)`$ is the normalized Voigt profile,

$$\varphi _a(x)=\frac{H(a,x)}{\sqrt{\pi }}=\frac{a}{\pi ^{3/2}}_{\mathrm{}}^{\mathrm{}}\frac{e^{t^2}dt}{(xt)^2+a^2}.$$
(3)
Adopting the notation of Hummer & Kunasz (1980), we define $`\tau `$ to be the mean optical scale, which increases in the negative $`z`$-direction through the slab. Therefore, $`d\tau =k_Ldz`$, which is related to the line center optical depth $`\tau _0`$ by, $`\tau _0=\varphi _a(0)\tau `$.

We assume that the continuum is purely absorbing with zero local emissivity. The source function then contains only the line terms, and can be written as (Hummer, 1969),

$$S_{iL}(\tau ,x)=\frac{1ϵ_i}{\varphi _{i,a}(x)}_{\mathrm{}}^+\mathrm{}R(x,x^{})J(\tau ,x^{})𝑑x^{}+G_i(\tau ),$$
(4)
where the first term represents the scattering term and $`G_i(\tau )`$ is the intrinsic source term. The quantity $`ϵ_i`$ is the destruction probability of the line per scattering (i.e., $`ϵ=0.203`$ for the N VII Ly$`\zeta `$ line) and $`J(\tau ,x)`$ is the angle-averaged intensity,

$$J(\tau ,x)=\frac{1}{2}_1^{+1}I(\tau ,x,\mu )𝑑\mu .$$
(5)
The scattering term is computed assuming partial redistribution in a Voigt profile, in which photons scatter coherently in the atoms’ frame. Compared to the assumption of complete redistribution, this provides a more accurate representation of line scattering in an optically thick medium where scattering in the damping wings is important. The frequency redistribution function $`R(x,x^{})`$ is defined as the probability that a photon of frequency $`x`$ absorbed by an ion is re-emitted at frequency $`x^{}`$, and can be written as,

$$R(x,x^{})=\frac{1}{\pi ^{3/2}}_{\mathrm{}}^+\mathrm{}e^{u^2}\left\{\mathrm{tan}^1\left[\frac{\mathrm{max}(x,x^{})+x}{a}\right]\mathrm{tan}^1\left[\frac{\mathrm{min}(x,x^{})x}{a}\right]\right\}𝑑u,$$
(6)
which was first derived by Henyey (1941) (see, also Hummer 1962, and references therein). Accounting for the angular redistribution makes negligible difference (Milkey, Shine, & Mihalas, 1975) and is, therefore, ignored. The intrinsic source term is frequency independent and can be produced, for example, through collisional excitation and or radiative cascades following recombination. The exact nature of the excitation mechanism is not important for our present purposes.

The transfer equation for multiple overlapping lines can then be written as,

$$\pm \mu \frac{dI_\nu (x,\mu ,\tau )}{d\tau }=\underset{i}{}\left[I(x,\mu ,\tau )\alpha _i(x)+(1ϵ_i)\frac{\alpha _i(x)}{\varphi _a(x)}_{\mathrm{}}^{\mathrm{}}R_i(x^{},x)J(\tau ,x^{})𝑑x^{}+\alpha _i(x)G_i(\tau )\right],$$
(7)
where $`\alpha _i(x)`$ represent the absorption coefficients normalized to that of the reference line at $`x=0`$, and are assumed to be independent of depth. Therefore, the first, second, and third terms on the right hand side of Eq. 7 represent absorption, scattering, and intrinsic emission, respectively.

The transfer equation is solved using the Feautrier method (Feautrier, 1964), which requires a discretized version of Eq. 7 in angular, frequency, and optical depth variables. Defining the total opacity $`\varphi _{\mathrm{tot}}(x)=\varphi _{i,a}(x)+\beta `$, where $`\beta `$ is the continuum opacity relative to the reference line opacity ($`\beta =k_C/k_L`$) assumed to be independent of frequency across the line, we define a mean-intensity-like quantity,

$$j_{\mu \nu }=\frac{1}{2}[I(x,+\mu ,\nu )+I(x,\mu ,\nu )],$$
(8)
and rewrite Eq. 7 as a second order differential equation,

$$\mu ^2\frac{d^2j_{\mu \nu }}{d\tau ^2}=\varphi _{\mathrm{tot}}^2(x)j_{\mu \nu }+\varphi _{\mathrm{tot}}(x)\underset{i=0}{}\alpha _i(x)S_i(\tau ,x).$$
(9)
The presence of temperature and ion abundance gradients will introduce an additional term on the right hand side, which is ignored for simplicity. We assume a symmetric slab and specify boundary conditions on the surface and at the midplane of the slab. Assuming no incident radiation on either boundaries, they can be written as,

$$\mu \frac{dj_{\mu \nu }}{d\tau }|_{\tau =0}=j_{\mu \nu }$$
(10)
on the surface and,

$$\mu \frac{dj_{\mu \nu }}{d\tau }|_{\tau =\tau _{\mathrm{tot}}/2}=0$$
(11)
at the midplane. These boundary conditions are also discretized using a second order method described by Auer (1967). The frequency integral is represented as a quadrature sum using Simpson’s formula with $`N_x=100200`$ points depending on the temperature and the total optical depth of the slab. We use a 2-point Gaussian quadrature for the angular integral in the interval $`0\mu 1`$ ($`N_\mu =2`$). The optical depth is discretized into 12 points per dex. Extensive testing shows that the above discretization scheme yields reliable results. Energy conservation (see, e.g., Hummer & Kunasz 1980) is satisfied to within $`2`$% for most cases studied in this paper, and is no larger than $`5`$% even in the worst cases.

## 4 Conversion Efficiencies

We solve the transfer equation for a source function distributed uniformly within a slab of ionized material for a range of total slab thicknesses. We define the O VIII Ly$`\alpha _1`$ line to be our reference line and measure frequency shifts in units of its Doppler width. The emissitivities of the O VIII Ly$`\alpha _1`$ and Ly$`\alpha _2`$ lines are assumed to be proportional to their respective statistical weights of the upper levels, i.e., $`G_{\mathrm{Ly}\alpha _1}(\tau )=2G_{\mathrm{Ly}\alpha _2}(\tau )`$, which is approximately correct for both collision-dominated and recombination-dominated line emission. The absolute numerical values for the source functions are not important for the present purposes, and without any loss of generality, we can write,

$$\underset{i}{}_0^{\tau _{\mathrm{tot}}}𝑑\tau _iG_i(\tau )1.$$
(12)
The solution to Eq. 9 – 11 yields the frequency-dependent intensity at each optical depth and angular points, which can then be used to compute the mean number of scatterings for each of the lines, their mean optical scales, and the escape probabilities.

Given the normalization condition (Eq. 12), the fraction of the original photons that are absorbed by a transition with destruction probability $`ϵ_i>0`$ can be expressed in terms of the mean number of scatterings (Hummer, 1969; Hummer & Kunasz, 1980). The fraction absorbed and destroyed by line $`i`$ can be written as,

$$f_{iL}=\frac{ϵ_i}{1ϵ_i}N_i=\frac{ϵ_i}{1ϵ_i}_0^{\tau _{\mathrm{tot}}}𝑑\tau _i_{\mathrm{}}^{\mathrm{}}\varphi _a(x)S_{iL}(\tau ,x)𝑑x,$$
(13)
where $`N_i`$ is the mean number of scatterings. Similarly, the fraction of photons absorbed in the continuum can be expressed in terms of the mean optical scale $`l`$ (Ivanov, 1973), i.e.,

$$f_C=\beta l=\beta _0^{\tau _{\mathrm{tot}}}𝑑\tau _{\mathrm{}}^{\mathrm{}}J(\tau ,x)𝑑x.$$
(14)
Finally, the fraction of photons that escape through both faces of the slab is simply,

$$f_{\mathrm{esc}}=_{\mathrm{}}^{\mathrm{}}𝑑x_0^1I(\tau =0,x,\mu )\mu 𝑑\mu ,$$
(15)
where $`I(\tau =0,x,\mu )`$ is the emergent intensity on the surface.

Fractional conversion efficiencies as a function of the total threshold optical depth at the O VIII edge ($`\tau _{\mathrm{O}\mathrm{VIII}}`$) at temperatures of $`kT=10\mathrm{eV}`$ and $`50\mathrm{eV}`$ are shown in Figures 4 and 5, respectively. The underlying continuum opacity is assumed to be $`0.1\tau _{\mathrm{O}\mathrm{VIII}}`$. At $`kT=10\mathrm{eV}`$, the line-center cross section of the O VIII Ly$`\alpha _1`$ line is $`6.9\times 10^{16}\mathrm{cm}^2`$ and is a factor of $`7.0\times 10^3`$ times larger than the corresponding continuum absorption cross section at threshold, which is assumed to be $`9.9\times 10^{20}\mathrm{cm}^2`$ for O VIII (Verner et al., 1996). For $`\tau _{\mathrm{O}\mathrm{VIII}}=1`$ and $`kT=10\mathrm{eV}`$ (Figure 4), only $`40`$% of the O VIII Ly$`\alpha `$ photons escape the medium, while $`40`$% are absorbed by N VII and $`20`$% are absorbed by the background continuum. The total line-center opacity in the O VIII Ly$`\alpha _1`$ line is $`6.9\times 10^3`$. We find the mean number of scatterings for the O VIII Ly$`\alpha _1`$ line to be $`2.3\times 10^3`$, which implies that thermalization through particle collisions is relevant if the gas density is higher than $`10^{18}\mathrm{cm}^3`$ (see §2). At a temperature of $`kT=50\mathrm{eV}`$, the overlap between the O VIII and N VII lines is larger, and the conversion to N VII is enhanced relative to the amount absorbed in the continuum.

The temperature dependence of the conversion efficiencies can be understood from the curves plotted in Figure 6. At low temperatures, the N VII Ly$`\zeta `$ line lies in the wings of the O VIII Ly$`\alpha `$ lines and so the conversion process is relatively inefficient. As the temperature is increased, the amount of overlap between the lines increases rapidly up to a temperature of $`kT40\mathrm{eV}`$, which is where the separation between the N VII Ly$`\zeta `$ and O VIII Ly$`\alpha _1`$ lines is approximately equal to one Doppler width. This temperature is representative of a photoionized plasma at this level of ionization. Above this temperature, the amount of line overlap increases more slowly than the temperature dependence of the line cross section, which decreases approximately as $`T^{1/2}`$, and so the efficiency drops again with temperature. Finally, we show in Figure 7 the effect of increasing the overlapping continuum opacity on the conversion efficiencies.

From the derived conversion efficiencies, one can estimate the emergent intensities of each of the lines for a given total optical depth. At $`kT=10\mathrm{eV}`$ and a total optical depth of $`\tau _{\mathrm{O}\mathrm{VIII}}=1`$, approximately 40% of the original O VIII Ly$`\alpha `$ photons escape through the surfaces of the slab, 40% of then are absorbed by N VII, and the remaining 20% are absorbed in the continuum (see Figure 4). Assuming that the medium is very highly ionized consisting only of H-like carbon, nitrogen, and oxygen, and further assuming that the emission coefficient ratios of the Ly$`\alpha `$ lines are proportional to their abundance ratios, (i.e., CNO Ly$`\alpha `$ relative line intensities of $`1.0:0.13:0.45`$), the emergent radiation field will have an O VIII Ly$`\alpha `$ line intensity of $`0.40`$, a N VII Ly$`\alpha `$ intensity of $`0.26`$, and a carbon line intensity of $`0.55`$. Here, we have simply assumed that 33% of the photons absorbed by N VII result in the N VII Ly$`\alpha `$ line and 50% of the photons absorbed by C VI produce the C VI Ly$`\alpha `$ line (see §2). Therefore, the oxygen to nitrogen line ratio decreased from 7.7 to 1.5 (a factor of $`5`$) and the oxygen to carbon line ratio decreased from 2.2 to 0.73 (a factor of $`3`$) simply due to finite opacity effects.

We do not attempt to compute the global emergent spectrum, which requires a self-consistent calculation of the O VIII Ly$`\alpha `$ line source functions including a complete set of ions and a realistic ionization balance calculation. To accurately compute the emergent CNO line intensities, one must properly account for all of the processes that increase the oxygen line source function. The forest of iron L-shell line emission shortward of the O VIII edge at $`\lambda =14.228`$ Å is particularly important and is likely to be the dominant contributor to the source function. A more detailed investigation will be presented in a future article.

## 5 Conclusions and Discussion

We have identified a pair of overlapping resonance lines, which alters the intensities of some of the most prominent lines in X-ray spectra of cosmic sources under optically thick conditions, analogous to the He II – O III Bowen fluorescence mechanism. A non-negligible fraction of the O VIII Ly$`\alpha `$ photons can be converted into N VII emission lines, which can be misinterpreted as an anomalous CNO abundance pattern. In general, oxygen emission lines will be suppressed, while both nitrogen and carbon lines will be enhanced compared to those emitted under optically thin conditions.

As briefly mentioned earlier, detections of non-solar CNO abundance ratios have been made in a variety of sources using soft X-ray data obtained with the Reflection Grating Spectrometer onboard XMM-Newton and the Chandra Low Energy Transmission Grating Spectrometer (see, e.g., Branduardi-Raymont et al. 2001; Kinkhabwala et al. 2002; Jimenez-Garate et al. 2002; Brinkman et al. 2002; Mason et al. 2003; Leutenegger, Kahn, & Ramsay 2003). In all cases, the nitrogen lines are observed to be stronger than expected relative to the oxygen lines. The carbon lines, on the other hand, are stronger in some sources and weaker in others. Although it is highly likely that non-solar overabundances play a major role in producing the anamolous line fluxes, it is also possible that a substantial part of it is due to the Bowen mechanism described in this paper. Detailed modeling and careful inspections of other lines in the observed spectrum are required to break the degeneracy between overabundance and radiative transfer effects.

Dynamical effects, such as turbulent motion and velocity gradients, which are not included in the present calculations, may reduce or enhance the conversion efficiency of O VIII Ly$`\alpha `$ into N VII depending on the geometrical configuration of the ionized medium. Turbulence, for example, can suppress the efficiency if the turbulent length scale is much smaller than the mean free path of the O VIII line photons. In the presence of velocity gradients, the efficiency can be enhanced in the direction where the N VII Ly$`\zeta `$ line is shifted into the O VIII Ly$`\alpha `$ line core. These effects coupled with density inhomogeneities will complicate the problem further and must be studied carefully on a case-by-case basis.

There are a few other potentially important line overlaps in the X-ray band that are worth mentioning. For example, one of the three brightest Fe XVII lines at wavelengths of 17.096 Å, 17.051 Å, and 16.780 Å typically referred to as the M2, 3G, 3F lines (Brown et al., 1998), respectively, coincide in wavelength with the high-$`n`$ series lines of O VII at 17.10068 Å ($`n=7`$), 17.02584 Å ($`n=8`$), etc., and 16.786 Å ($`n=\mathrm{}`$). In this case, O VII dominates the line opacity, while Fe XVII contributes most of the intrinsic source function. Another example is the overlap between the Fe XVIII lines at 16.071 and 16.004 Å (Brown et al., 2002) with the O VIII Ly$`\beta `$ lines at 16.00666 Å and 16.00552 Å. These examples are certainly not exhaustive and it is highly likely that they must all be accounted for collectively for accurately predicting the global X-ray spectrum of optically thick sources.

The author thanks Roger Blandford, Steven Kahn, and Duane Liedahl for valuable discussions, and Mingfeng Gu for his help with the Flexible Atomic Code. This work was supported by NASA through Chandra Postdoctoral Fellowship Award Number PF1-20016 issued by the Chandra X-ray Observatory Center, which is operated by the Smithsonian Astrophysical Observatory for and behalf of NASA under contract NAS8-39073.


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# Ferromagnetism and metallic state in digital (Ga,Mn)As heterostructures

## I Introduction

(Ga,Mn)As Ohno1  is the prototype of a new class of magnetic materials named diluted magnetic semiconductors (DMS) Ohno2 ; Ohno3 . These are obtained by doping ordinary semiconductors with transition metals. In the case of (Ga,Mn)As the Mn ions occupy the Ga sites and provide both localized spins ($`S`$=5/2) and holes. The spin holes are then antiferromagnetically coupled to the Mn ions and this gives rise to hole-mediated long range ferromagnetism via a Zener-like mechanism Dietl .

The potential impact of this material on the semiconductor industry is huge, since it opens the possibility of adding ferromagnetism to the AlAs/GaAs system, an important step toward the implementation of the spin degree of freedom in an electronic device Prinz . To date several concept devices have been demonstrated, including spin polarized light emitters Aws1  and electrically controlled ferromagnetism Aws2 , and one can envision (Ga,Mn)As among the building blocks for a spin-based quantum computer scheme DDV .

Despite these indisputable successes the critical temperature ($`T_C`$) of (Ga,Mn)As hardly exceeds 110 K Ohno2 ; Ohno3  and this poses severe limitations to future commercial applications. At present low temperature annealing processing has allowed an increase of the Curie temperature from 110 K to about 170 K not ; nit , but room temperature ferromagnetic (Ga,Mn)As appears difficult to produce. However these recent annealing experiments have demonstrated an important point: the low critical temperature of (Ga,Mn)As is not an intrinsic limitation of the material, but is affected by the inability to control the Mn and holes concentration independently.

A possible way to improve the control over the electronic and magnetic interactions is to produce magnetic semiconductor superlattices. These are the digital ferromagnetic heterostructures (DFH), which are obtained by $`\delta `$-doping with Mn a low temperature GaAs MBE-grown layer Kaw1 . Here Mn concentrations as high as 50% are obtained in a few (typically 2-3) GaAs monolayers and one may expect correspondingly higher large Curie temperatures. However these structures show properties rather different from those of their random alloy counterparts. Here we report the most relevant experimental findings.

1) The Curie temperature is rather low ($`50`$ K) and independent of the separation between the Mn planes Kaw1 . $`T_c`$ usually decays with increasing GaAs layer thickness separating the MnAs sub-monolayers, and saturates for thicknesses larger than $``$50 GaAs monolayers. The saturation is unexpected according to the mean field model for three dimensional systems, since the total Mn concentration in the sample decreases with the increase of the GaAs thickness Dietl . This separation dependence suggests that DFH behave like planar systems.

2) Hall measurements in the direction parallel to the MnAs planes show an anomalous Hall effect for undoped samples, which disappears upon Be doping gwin1 ; gwin2 . Large Shubnikov de Haas oscillations are found in doped samples, although surprisingly the carrier densities extracted from the Hall coefficient and from the Shubnikov de Haas oscillations are different. This suggests that two different carrier types could be present in the system.

3) There is a correlation between metallicity and Curie temperature. In low $`T_C`$ samples the transport is given by activated hole conduction and this is consistent with variable range hopping in two dimensions Luo ; mc2 ; Ted . In contrast, in the only DFH to date showing $`T_C`$ around room temperature the transport is $`p`$-type and metallic McCombe . However in these latter structures made from (Ga,Mn)Sb two phases may be present mc2 ; McCombe , with a diluted phase responsible for the ferromagnetism below 40 K and a zincblende MnSb phase responsible for the room temperature ferromagnetism.

4) GaAs/AlAs band engineering and spatial selective doping Tanaka ; Furdyna  allow the enhancement of the $`T_C`$ in AlAs/(Ga,Mn)As DFH with respect to their GaAs/(Ga,Mn)As counterparts. This enhancement is correlated with the enhanced hole concentration in the Mn layers and to the achievement of metallic conductance.

Finally we point out that some of the aspects described above are common to other $`\delta `$-doped structures. For instance it has been recently demonstrated Noh  that Be $`\delta `$-doped low temperature GaAs undergoes an insulator to metal transition as the Be concentration is enhanced. In this case the transport changes from $`n`$-type thermally activated, to $`p`$-type metallic. The first is reported for small Be concentrations and is due to the hopping between As antisite levels in the GaAs region, while the second dominates at large Be concentrations and is due to extended hole states in the Be rich region.

From this brief overview it is clear that DFH present rather rich and complex physics, which calls for an extensive theoretical analysis. So far the magnetic properties of DFH have been studied only within the mean field approach Meyer ; Sham , while the transport has been investigated solely in the ballistic limit for the case of 100% Mn doping in the plane usprl . Here we report an extensive ab-initio study of the electronic, magnetic and transport properties of both GaAs/(Ga,Mn)As and AlAs/(Ga,Mn)As DFH, for various Mn concentrations and As antisite doping levels.

The paper is organized as follows. In the next section we describe our computational technique and we motivate the approximations made. Then we investigate the properties of GaAs/(Ga,Mn)As DFH, the effects of As antisites, and the properties of AlAs/(Ga,Mn)As DFH. Finally we conclude and we suggest new ways to manipulate the properties of DFH.

## II Computational Technique

We perform density functional theory (DFT) kohn  calculations within the local spin-density approximation (LSDA). The use of LSDA for DMS is very well documented usreview , and it provides a good description of the main physics of (Ga,Mn)As. Recently we have demonstrated alessio  that self-interaction corrections to the LSDA do not strongly affect the band structure of (Ga,Mn)As, although they lead to strong localization and orbital ordering of the Mn $`d`$ shell in (Ga,Mn)N. For this reason we choose to work within the LSDA.

Our numerical implementation, contained in the code SIESTA Siesta1 ; Siesta2 , uses pseudopotentials and a highly optimized localized atomic orbital basis set. These two aspects make SIESTA extremely suitable for handling systems with a large number of atoms in the unit cell without a significant loss of accuracy. The drawback is that both the pseudopotentials and the basis set must be accurately optimized.

First we consider the pseudopotentials. We use well-tested scalar relativistic Troullier-Martins pseudopotentials TM  with non linear core corrections Lou82  and Kleinman-Bylander factorization KB1 . The eigenvalues for the valence electrons of the free atom are compared with those generated for an all-electron calculation for different atomic and ionic configurations. Then we perform total energy calculations for elementary solids comparing the lattice constant, the bulk modulus and the band structure with reference calculations. These are performed with a well-converged basis set. Note that this is quite a delicate procedure, since with localized orbital basis sets the variational principle is not governed by a single-parameter such as the cut-off energy with plane-waves.

Finally an optimized basis set is selected. The basis functions in SIESTA are the product of an angular function with a given angular momentum, and a radial numerical function. This latter is constructed as the DFT solution of the free pseudo-atom with an additional hard-wall confining potential. Furthermore, in order to enhance the variational freedom, several radial functions (“zetas”) for the same angular momentum are constructed with the ‘split valence’ scheme emilio . In the case of (Ga,Mn)As the crucial aspect is to introduce several zetas for the Mn $`d`$ orbitals, and the criterion we have adopted is that of reproducing the physics of the $`d`$ shell of Mn in MnAs. More details are given in reference usprb . Here we only mention that the same procedure has been adopted for the Al pseudopotential and basis set. These have been checked for both metallic Al and zincblende AlAs. The reference configuration for the pseudopotential is 3s23p1 with cut off radii 1.90, and 1.80 a.u. respectively for the $`s`$ and $`p`$ shells. Finally the basis set for Al has two basis functions for both $`s`$ and $`p`$ electrons, with the same cut-off radius of 6.0 a.u. and the ‘split norm’ parameter is 0.15 Siesta2 .

All the calculations presented here are performed within a supercell scheme. Our supercell is constructed from a $`2\times 2\times 3`$ zincblende cubic cell (lattice constant $`a_0`$=5.65Å) and contains 96 atoms in total. We mimic a DFH by replacing Ga with Mn ions only in one of the GaAs planes. We use periodic boundary conditions in all directions sampling 18 $`k`$-points in the supercell Brillouin zone. This corresponds to a (Ga,Mn)As/GaAs superlattice in which the (Ga,Mn)As planes are separated by 6 GaAs monolayers (16.95Å). In this supercell the Mn ions can occupy only eight possible positions in plane. These are arranged into two simple cubic lattices translated with respect to each other along the diagonal of the $`xy`$ plane. Since the exact positions of the Mn ions is rather important in determining the electronic structure, these are schematically presented in figure 1.

## III (Ga,Mn)As DFH

In this section we analyze the effects of the Mn concentration on the electronic properties of (Ga,Mn)As DFH, by calculating the band structure, the DFT total potential, the strength of the FM coupling and the transport properties. Our main aim is to monitor the evolution of these quantities as a function of the Mn concentration in the (Ga,Mn)As plane. In particular we want to establish whether there is a correlation between the Mn concentration and the metallicity of the system.

### III.1 Band structure

In figure 2 we present the band structure of our (Ga,Mn)As/GaAs DFH for Mn concentrations of 12.5%, 25% and 50%. In figures 2a, 2b and 2c, only the sites belonging to one of the two cubic sub-lattices in the plane are occupied. This maximizes the mean Mn-Mn separation. In contrast in figure 2d sites belonging to both the lattices are occupied (namely A1, A2, A3, and B1).

Here we plot the bands only along two directions parallel to the (Ga,Mn)As plane, since in the perpendicular direction these are very similar to the case of MnAs planes embedded in GaAs usprl  and they do not change significantly with the Mn concentration. In contrast for directions parallel to the Mn planes, we expect a transition from the band structure of a (Ga,Mn)As random alloy to the metallic band structure of a zincblende MnAs plane usprl . This is indeed the behavior observed in figure 2. If one increases the Mn concentration from 12.5% to 50% (from (a) to (b) to (c)) the Fermi level shifts downward in energy ending up deep in the majority spin valence band. At the same time also the spin-splitting of the valence band increases. Note that the DFH behaves as an half-metal at every concentration. The magnetic moment of the supercell therefore is always $`4\mu _\mathrm{B}\times N_{\mathrm{Mn}}`$ where $`N_{\mathrm{Mn}}`$ is the number of Mn atoms in the cell. Mülliken population analysis usprb ; Mul  shows an orbital population for the Mn $`d`$ shell of $`4.7`$ for the majority spin electrons and of $`0.8`$ for the minority, although both depend on the specific spatial arrangement of the Mn ions. These aspects are consistent with the picture of Mn as a single acceptor in GaAs. The Mn ions are in a $`d^5`$ state with an associated antiferromagnetically coupled hole, as for the case of the random alloys usprb .

However the situation of figure 2d is in stark contrast with this picture. In this case the Mn concentration is still 50% but three of the four Mn ions in the plane occupy nearest neighbor positions. The band gap in the majority spin band closes and the material is an half metal with a completely metallic majority spin band. This suggests that the actual position of the Mn atoms in the plane is crucial in determining the electronic properties. The same sensitivity of the electronic structure to the position of the Mn ions is also present in the random alloys usapl . However this generally does not lead to a strong distortion of the band structure, and the bands obtained for Mn ions diluted in the supercell or occupying nearest neighbor positions are quite similar. In DFH the planar arrangement of the Mn ions makes the system more confined, and therefore more sensitive to inhomogeneities. This of course drastically affects the scattering properties of electrons in the (Ga,Mn)As planes, as we will show in the following sections.

### III.2 DFT potential

One fundamental question for understanding the physics of DFH is: “are the spin carriers confined in the (Ga,Mn)As plane or do they spread over the GaAs spacer?”. In order to answer this question it is useful to investigate the behavior of the total DFT potential along the superlattice direction $`z`$. This of course has the same periodicity as the atomic lattice. However we are not interested in the potential at the atomic scale, and instead we perform a “macroscopic average” Bald . The macroscopic average is obtained by first taking a planar average and then by averaging the result over the period of a GaAs monolayer along the superlattice direction. The resulting $`z`$-dependent potential is that felt by an electron with long wave-length at a density small enough not to perturb significantly the potential. Therefore this can be interpreted as the effective $`z`$-dependent potential in the spirit of the envelope function approximation.

In figure 3 we plot the macroscopic average for the total DFT potential, the Hartree potential and the charge density distribution as a function of the position along the superlattice direction for different Mn concentrations.

Notice first that there is indeed a confining potential in the Mn plane. The charge density is unevenly distributed along the superlattice and accumulates in the Mn plane. This is consistent with the picture of the Mn ions that we have given in the past usprb , in which the majority spin hole is nearly bound to the Mn ion while the minority feels a much weaker potential.

The $`z`$-dependent total potential is strongly spin-dependent. Generally it has a double well structure, with two potential minima, located in the (Ga,Mn)As plane and in the GaAs spacer respectively. These are separated by a potential barrier which grows if the Mn concentration in the plane increases. We further investigate the nature of the confining potential by calculating its evolution upon increasing the Mn doping. For this purpose we define $`\mathrm{\Delta }_1^\sigma `$ and $`\mathrm{\Delta }_2^\sigma `$ as the energy minima in in the (Ga,Mn)As plane and the GaAs spacer respectively measured with respect to the top of the energy barrier (see figure 4). $`\sigma `$ is the spin index and $``$ ($``$) indicates the majority (minority) spin electrons.

We denote as $`\mathrm{\Delta }_1^\mathrm{H}`$ and $`\mathrm{\Delta }_2^\mathrm{H}`$ the same quantities for the Hartree potential.

In figure 5 we present these quantities as a function of the number of Mn ions in the Mn plane (the maximum number is 8). First we notice that for minority spins both $`\mathrm{\Delta }_1^{}`$ and $`\mathrm{\Delta }_2^{}`$ mimic closely the behavior of the Hartree potential (figure 5a, and 5b).

This means that the DFT potential for the minority spins is largely electrostatic with small contributions from the exchange part. In contrast $`\mathrm{\Delta }_1^{}`$ for the majority electrons deviates strongly from the behavior of its electrostatic component, and the deviation increases as the Mn concentration is enhanced.

If we now compare $`\mathrm{\Delta }_1`$ with $`\mathrm{\Delta }_2`$ for the two spin species we find a rather different behavior. For the majority spin electrons (figure 5c) $`\mathrm{\Delta }_1>\mathrm{\Delta }_2`$ at all Mn concentrations. Furthermore the difference $`\mathrm{\Delta }_1\mathrm{\Delta }_2`$ increases with increasing the Mn concentration. This means that the minimum in the (Ga,Mn)As plane is always the lower of the minima for majority electrons and it becomes more stable as the Mn concentration increases.

In contrast, for the minority electrons there is not a striking difference between $`\mathrm{\Delta }_1`$ and $`\mathrm{\Delta }_2`$ meaning that they are less confined in the (Ga,Mn)As plane (see figure 5d). It is also interesting to point out that $`\mathrm{\Delta }_2>\mathrm{\Delta }_1`$ at low Mn concentration but there is a cross over for doping of the order of 50%. This is suggestive of the fact that the confinement of minority electrons switches from the GaAs to the (Ga,Mn)As region upon the increase of Mn concentration. Of course there are no empty minority spin states at the Fermi level and therefore in these structures the minority spins contribute little to the electron transport. However in the case of additional doping (for instance by intrinsic As antisites, AsGa) an impurity band may form at the Fermi level, opening a transport channel in the minority sub-band. The potential described here suggests that those electrons will hardly distribute over the (Ga,Mn)As plane at low doping but they will invade the (Ga,Mn)As region at large Mn doping. For this reason we expect a spatial separation of the spin currents (majority spin in the (Ga,Mn)As plane, and minority spin in the GaAs spacer) for low concentrations, and strong spin-mixing at higher concentrations.

### III.3 Stability of the ferromagnetic state

In this section we investigate the strength of the ferromagnetic coupling in (Ga,Mn)As DFH, and in particular we discuss how the coupling depends on Mn doping. The relevant quantity to investigate is the energy difference $`\mathrm{\Delta }_{\mathrm{FA}}=E_{\mathrm{AF}}E_{\mathrm{FM}}`$ between the total energy of the antiferromagnetic ($`E_{\mathrm{AF}}`$) and the ferromagnetic ($`E_{\mathrm{FM}}`$) configurations of the supercell. Here we investigate the case of 25%, 37.5% and 50% Mn doping in the plane, where respectively two, three and four Mn ions are present in the supercell. This gives us some freedom to arrange the Mn ions in different ways and to investigate different antiferromagnetic configurations. A summary of the cases studied is presented in table 1.

We ran a total energy calculation for each of the configurations of table 1, and fit our calculations to a third nearest neighbors Heisenberg model, in which the total energy $`E`$ is expressed as

$$E=\underset{i<j}{\overset{\mathrm{nn}}{}}J_{ij}\stackrel{}{S}_i\stackrel{}{S}_j.$$
(1)
$`J_{ij}`$ are the exchange constants, $`\stackrel{}{S}_i`$ is the spin of the $`i`$-th Mn ions, and the sum runs up to third nearest neighbors. The results of this fit are presented in table 2, where by convention we use $`|\stackrel{}{S}|=5/2`$. Note that in our fitting procedure we have more configurations than parameters, and it is remarkable to observe that the fit is generally very good.

From the table it is clear that the first nearest neighbor coupling constant, $`J_1`$, is responsible for most of the coupling which decays rapidly with the Mn-Mn separation. It is also interesting to note that the second nearest neighbor coupling, $`J_2`$, is small for all the concentrations studied. Remarkably, all the coupling constants are strongly dependent on the Mn concentration in the plane, and they decay quickly as this is increased. This decay, which is particularly severe for the first nearest neighbor coupling constant, is in stark contrast with the expectations of RKKY-like theories in which the $`J`$’s increase as $`x^{1/3}`$ at zero temperature MCD1 . However it is consistent with previous DFT-LDA calculations Mark  for DMS random alloys, and illustrates once again the critical dependence of the Mn-Mn ferromagnetic coupling on the local chemical environment.

In order to put our calculations in perspective, next we estimate the ferromagnetic Curie temperature, $`T_C`$, of the system for different Mn concentrations. This can be simply obtained by using the mean field expression for a three dimensional Heisenberg model, which reads

$$T_Ck_B=\frac{2}{3}S^2n_{\mathrm{Mn}}\underset{i}{}J_i,$$
(2)
where $`n_{\mathrm{Mn}}`$ is the Mn concentration, and the sum runs over all the cation sites. This is a rather crude approximation and a complete thermodynamic theory should include the elementary spin-excitations MacDonspex ; Bhattspex . Moreover in the present case the Mn concentration is not a well-defined quantity since the (Ga,Mn)As region cannot be separated from the GaAs region. Roughly speaking one should consider the volume of (Ga,Mn)As to be the region around the Mn ions as thick as the range of the relative confining potential (see figure 3). This quantity is not clearly defined. Therefore, assuming that the (Ga,Mn)As volume does not depend on the Mn concentration, we prefer to evaluate only the following “magnetic energy”

$$E_{\mathrm{mag}}=x\underset{i}{}J_i,$$
(3)
which is proportional to the Curie temperature.

From table 2 one notes that $`E_{\mathrm{mag}}`$ has a non-monotonic dependence on the Mn concentration, presenting a maximum for $`x=0.375`$. Such behavior is generally observed in DMS random alloys, for which there is a maximum of $`T_C`$ upon Mn doping, followed by a sharp decay for large Mn concentrations (above $`x=0.05`$) Ohno2 ; Ohno3 . This usually coincides with the loss of the metallic state. In contrast, in DFH made to date the situation seems to be reversed Kaw1 , with a larger $`T_C`$ for larger Mn concentrations. This apparently contradicts our predictions. However two important aspects need to be considered. First in actual DFH the transport is through variable range hopping Ted , while in our supercell calculations the system is “by definition” metallic. Secondly DFH usually present very strong compensation. This indicates that a large number of donors, whose density is probably related to the in plane Mn concentration, are present in the DFH. In the next sections we will investigate systematically both the transport properties and the effects of the presence of donors.

### III.4 Ballistic Transport

In this section we investigate the ballistic transport in DFH, with the aim of understanding the nature of the electronic states responsible for the conductance. The technique used is identical to that described in references usprl ; uslb  and here we summarize only the main aspects. The transport is calculated by using the self consistent tight-binding like Hamiltonian and overlap matrix computed by SIESTA. The matrix elements are obtained from the self-consistent charge density by evaluating numerically both two- and three-center integrals Siesta2 . Then we rewrite both the Hamiltonian and the overlap matrix in a tridiagonal form along the direction of the transport and we use periodic boundary conditions along the other directions. Finally, the $`k`$-dependent transmission matrix $`t_\sigma (k)`$ for the spin direction $`\sigma `$ is calculated by using our Green’s function technique uslb , and the spin conductance $`\mathrm{\Gamma }^\sigma `$ in the Landauer-Büttiker formalism lb ,

$$\mathrm{\Gamma }^\sigma =\frac{e^2}{h}\underset{k}{\overset{\mathrm{BZ}}{}}\mathrm{Tr}t_\sigma (k)t_\sigma (k)^{},$$
(4)
where we integrate over the two-dimensional Brillouin zone in the plane orthogonal to the direction of the transport. Here we consider a two spin fluid model, where there is no mixing between the majority and minority spin currents.

We study transport only in the direction parallel to the Mn plane. In the orthogonal direction in fact the transport is mainly due to hopping between the Mn planes and it is strongly suppressed if these are sufficiently far apart usprl . In figure 6 we present the conductance as a function of energy for a 50% Mn supercell respectively in the FM state, with the Mn ions uniformly distributed in the plane (configuration FM1 of table 1).

As expected from the band structure (figure 2c) the conductance as a function of energy shows an half-metallic behavior, with zero conductance for the minority spin band at the Fermi level. This 100% spin polarization of the conductance persists down to 0.5 eV from the Fermi energy, where minority states at the top of the valence band start contributing to the current. Turning our attention to the orbital contribution to the conductance it is important to observe that, at the Fermi level the current is entirely due to a mixture of As $`p`$ and Mn $`d`$ $`t_2`$ states. It is also interesting to note that non-negligible Mn $`d`$ contributions are present in the majority spin band for energies down to 4 eV below the Fermi level. This is an indication of the strong $`p`$-$`d`$ hybridization in the majority spin band, and in particular at its top. In contrast the Mn $`d`$ contribution to the conductance is almost negligible in the valence minority band, and Mn $`d`$ states appear only for $`E3`$ eV, relative to the bottom of the conduction band.

This 100% spin-polarization at the Fermi level is very encouraging for the potential use of DFH as spin-injector for spintronics devices. However it is crucial to investigate how this feature survives when compensating defects are present in the system.

## IV (Ga,Mn)As DFH: effects of AsGa

As in the case with the (Ga,Mn)As random alloys, DFH are also usually strongly compensated so that the hole concentration is considerably lower than the Mn concentration. It is generally accepted that the strong compensation is due to donors, most likely of intrinsic defects. In particular both As antisites (AsGa) Ohno3 ; usapl  and interstitial Mn (Mni) mninter1 ; mninter2  have been indicated as relevant compensating defects. The relative abundance of those donors probably depends on the growth conditions, the Mn concentration, and the post-growth processing. Since DFH are usually grown under large As overpressure Kaw1  we believe that in this case As antisites dominate. Here we investigate how the electronic properties of a 50% Mn DFH changes upon AsGa doping.

### IV.1 Band Structure

As in the previous section the band structure provides important information on the electronic properties of the DFH. In figure 7 we present the band structure for 50% in plane Mn DFH, where a single AsGa is introduced into the GaAs spacer at midway between two consecutive (Ga,Mn)As planes (the total AsGa concentration is $``$2%).

The most important feature of this band structure is that the half-metallic state is destroyed. This is due to the appearance of the AsGa level in the minority spin band, and to the fact that the Fermi energy is pined at this level. An As antisite in GaAs is a double donor with a doubly occupied deep level at midgap and an empty resonant state at the edge of the conduction band. These states have respectively the A and T2 symmetries of the $`T_\mathrm{d}`$ point group usjmmm . In (Ga,Mn)As the density of such defects is generally rather large and they can give rise to the formation of narrow impurity bands. In addition in the case of DFH it is likely that the As antisites will concentrate in the proximity of the Mn layers. This is confirmed by our total energy calculations, which show that there is an energy gain of approximately 0.9 eV when an As antisite moves from the middle of the cell to the Mn plane.

The total magnetic moment of such a unit cell is about 17.2$`\mu _\mathrm{B}`$ and depends weakly on the position of the As antisite with respect to the Mn plane (it is 17.33$`\mu _\mathrm{B}`$ when the AsGa lies in the (Ga,Mn)As plane). Assuming a rigid band model and considering that, in absence of As antisites the magnetic moment of the cell is 16$`\mu _\mathrm{B}`$, we conclude that an AsGa contributes 0.4 electrons to the minority band and 1.6 to the majority (we recall that one AsGa also introduces an impurity state that can accommodate two electrons). Therefore the presence of one As antisite in such a unit cell has two main effects: i) it compensates up to 1.6 holes in the majority spin band, and ii) it opens a conduction channel at the Fermi level in the minority spin band. This is a crucial aspect for understanding the transport properties of such structures.

### IV.2 Transport in presence of As antisites

We calculate the in plane ballistic conductance for a 50% Mn DFH with one AsGa in the middle of the spacer and the Mn ions uniformly distributed in the plane (configuration FM1). This is the same situation as in figure 6. The results are presented in figure 8, where again we have considered up to 100 $`k`$-points in the transverse Brillouin zone.

The main difference with respect to the AsGa-free case is the presence of a non-vanishing conductance for the minority spin electrons at the Fermi energy. This is entirely due to the AsGa impurity band as pointed out in the previous section, and of course destroys the half-metallic behavior of the spin current. The spin-polarization of the current $`P`$, defined as

$$P=\frac{\mathrm{\Gamma }^{}\mathrm{\Gamma }^{}}{\mathrm{\Gamma }^{}+\mathrm{\Gamma }^{}},$$
(5)
where the conductances are taken at the Fermi level, drops from 100% in the defect-free case to about 60% in the present case.

However the situation is rather different if we consider diffusive transport mazin . This is due to the different way in which the density of states and the group velocity contribute to the conductance in the ballistic and diffusive limits. In fact, in the ballistic limit the conductance of a uniform system can be obtained simply by summing up the number of scattering channels at the Fermi level

$$\mathrm{\Gamma }^\sigma =\frac{e^2}{h}\underset{k}{\overset{\mathrm{BZ}}{}}1=\frac{e^2}{h}\underset{k}{\overset{\mathrm{BZ}}{}}N_k^\sigma v_k^\sigma =\frac{e^2}{h}Nv^\sigma ,$$
(6)
where $`N_k^\sigma `$ and $`v_k^\sigma `$ are respectively the density of state and the group velocity for a spin $`\sigma `$ scattering channel, and the sum is performed over the two dimensional Brillouin zone orthogonal to the transport direction. In contrast from the classical Boltzmann equation one finds that the diffusive spin conductance is proportional to

$$\tau ^\sigma Nv^2^\sigma =\tau ^\sigma \underset{k}{}N_k^\sigma v_{k}^{\sigma }{}_{}{}^{2},$$
(7)
where now the sum runs over the three dimensional Fermi surface and $`\tau ^\sigma `$ is the spin-dependent relaxation time mazin . This reflects the well-known fact that, while in the ballistic limit all the scattering channels contribute with $`e^2/h`$ to the conductance independently from their group velocity, in the diffusive case the current is dominated by fast electrons because of the $`v^2`$ dependence.

If one assumes that the relaxation time is not dependent on the spin direction ($`\tau ^{}=\tau ^{}`$), then the spin polarization of the current in the diffusive limit can be written as

$$P_{Nv^2}=\frac{Nv^2^{}Nv^2^{}}{Nv^2^{}+Nv^2^{}}.$$
(8)
In general $`P`$ and $`P_{Nv^2}`$ are different, with $`P_{Nv^2}`$ larger if the difference in conductance for the two spin channels originates from a large Fermi velocity mismatch between the two spin bands. This is the case in the present DFH. In the majority band the Fermi surface is derived from the top of the GaAs valence band and the Fermi velocity is rather large. In contrast the minority band Fermi surface is due to the As antisite impurity band and the Fermi velocity is quite small. Therefore, since in the diffusive limit the conductance is proportional to $`v^2`$, we expect a much larger spin polarization of the current compared with the ballistic case.

In figure 9 we present $`Nv^2`$ as a function of energy for the same DFH as that of figure 8. The spin polarization at the Fermi energy is now 80%. Since in actual DFH the transport is due to hopping conductance Ted , we can conclude that As antisites, although they destroy the half-metallic state do not strongly affect the spin-polarization of the current.

Finally it is interesting to study the spatial distribution of the current across the DFH in the presence of As antisites. In figure 10 we present the real space charge density distribution, $`\rho (𝐫)`$, calculated only for those states contributing to the conductance at the Fermi energy usprl . Strictly speaking this does not represent the current distribution in real space, but gives information on the spatial distribution of the conductance electrons’ wave functions around $`E_\mathrm{F}`$.

The main feature of figure 10 is that there is a spacial separation between the two spin currents, with the majority spin current located near the Mn plane, and the minority current strongly localized around the As antisites. The first is evenly distributed and this is suggestive of a metallic like behavior, while the second is strongly localized at the scattering center, suggesting an hopping-like transport. Moreover, if we correlate the spin current with the relevant band-structure (see figure 7), we notice that the majority spin-current is hole-like, while the minority is electron-like.

We also investigate how these features change when the As antisite moves toward the Mn plane. Although the conductance as a function of energy does not present any significant modifications with respect to the case of figure 7, the spacial distribution shows an increased participation of the As antisite in the majority spin conductance as it moves closer to the Mn plane. This suggests that As antisites can play an important rôle in spin relaxation processes within DFH.

In conclusion, our transport results suggest that, if there is no spin mixing, the transport is dominated by a $`p`$-type metallic-like majority spin current with a smaller contribution from an $`n`$-type hopping-like minority spin current. Moreover the two spin-currents are spatially separated, preventing spin-mixing, only if the As antisites are reasonably far from the Mn plane.

### IV.3 Fit to the Heisenberg Model

We now investigate the stability of the ferromagnetic state when As antisites are present. We perform similar calculations to those described in section IIIC, but this time we include one AsGa in the unit cell. Since the relative position of the AsGa with respect to the Mn ions is crucial in determining the electronic and magnetic properties usapl , we investigate how the coupling depends on the As antisite position along the superlattice direction.

In figure 11a we present the value of the exchange constant for first, second and third nearest neighbor couplings as a function of the position of the As antisite with respect to the Mn plane. In the same figure we also present the same values for the As antisite-free case and for the case of two As antisites (located respectively at 1/3 and 2/3 of the supercell along the superlattice direction).

From the figure it is clear that, in all cases, most of the coupling comes from nearest neighbor interaction, which accounts on average for 75% of the total coupling $`J_{\mathrm{tot}}=_iJ_i`$. Then there is a fast decay of the exchange coupling with separation. This coupling is therefore short range. Furthermore it is very interesting to note that the second nearest neighbor coupling (Mn ions at A1 and A2) is almost negligible in all cases, and it sometimes assumes negative values. This suggests possible local antiferromagnetic coupling between the Mn ions as recently demonstrated experimentally mc2 .

Turning our attention to the effect of As antisites, it is clear that these weaken the coupling between the Mn ions. This is expected since an AsGa is a donor and therefore its presence partially compensates the free holes responsible for the long range ferromagnetic coupling. However our accurate supercell calculations bring additional interesting features. In agreement with the case of the random alloys (see reference usapl ), the actual position of the As antisite with respect to the Mn ions determines most of the properties. From figure 11 it is clear that the ferromagnetic coupling is weakened when the As antisite moves toward the Mn plane. In particular the exchange constants for the cases when $`z=1/6`$ and $`z=0`$, are very similar to those of the case of two As antisites ($`z=1/3`$ and $`z=2/3`$). This feature can be understood by considering the potential profile discussed in the previous section. In fact the charge is strongly confined in the Mn plane with a potential barrier separating the plane from the GaAs region. Therefore it is natural to think that any perturbation in the GaAs region will only weakly affect the electronic configuration of the Mn plane, unless such a perturbation is spatially located in the vicinity of such a plane.

In the second half of figure 11 we present the magnetic energy, $`E_{\mathrm{mag}}=x_iJ_i`$, for the different cells investigated. As we pointed out previously this quantity is proportional to the Curie temperature, $`T_C`$. From the figure it is clear that $`E_{\mathrm{mag}}`$ depends sensitively on the presence of the As antisites and on their actual location. In particular, although we find the lowest value of $`E_{\mathrm{mag}}`$ in the case in which two As antisites are present, we also find that this is very similar to the case of a single As antisite located in close proximity to the Mn plane ($`z=1/6`$ in the present case). Therefore we conclude that one can obtain high Curie temperatures, not only by avoiding the formation of intrinsic defects, but also by controlling their position with respect to the magnetic region.

Finally we make a few comments on the effect of disorder. Since in actual samples we are not able to control the exact position of the Mn ions with respect to each other, and since the Mn-Mn coupling is strongly dependent on the relative positions of the Mn ions and those of the As antisites, it is likely that there are regions of strong Mn-Mn coupling together with regions of weak or even antiferromagnetic coupling. This suggests that in addition to configurational disorder, magnetic disorder can also be present in DFH even at low temperatures. Therefore since the electrons (or holes) at the Fermi level have a rather large (metallic) density, and are strongly confined in a few atomic planes around the Mn ions, we can conclude that DFH have the electronic properties of highly resistive (dirty) metals. Turning the argument around, we conclude that the metallicity is crucial for the magnetic state of DFH, and that the most metallic samples are likely to show less magnetic disorder and therefore more robust magnetic properties McCombe .

## V AlAs/(Ga,Mn)As heterostructures

One of the main messages from the analysis done so far is that the exchange part of the DFT potential creates a strong confinement potential for the majority electrons in the Mn plane. In this section we investigate the effects of an additional confining potential, namely that obtained by sandwiching a (Ga,Mn)As monolayer into the GaAs region of an AlAs/GaAs superlattice. Our expectation is that the AlAs/GaAs band alignment will further confine the spin-holes in the proximity of the Mn ions, therefore enhancing the exchange coupling.

### V.1 GaAs/AlAs band alignment

Before considering the Mn-doped case we first illustrate the general band alignment of an AlAs/GaAs superlattice, as obtained from our DFT calculations. The valence band off-set, $`\mathrm{\Delta }`$, is calculated as suggested by Baroni et al. Baroni  as

$$\mathrm{\Delta }=\mathrm{\Delta }E_v+\mathrm{\Delta }V,$$
(9)
where $`\mathrm{\Delta }V`$ is the off-set between the AlAs and the GaAs electrostatic potentials calculated for an AlAs/GaAs heterostructure, and $`\mathrm{\Delta }E_v`$ is the energy difference between the valence band tops, $`E_v`$, of the bulk materials. These are calculated from their electrostatic potential $`V`$

$$\mathrm{\Delta }E_v=\left(E_vV\right)_{\mathrm{GaAs}}\left(E_vV\right)_{\mathrm{AlAs}}.$$
(10)
Here we have constructed a supercell by stacking four AlAs cubic cells on top of four GaAs cubic cells, all with the same GaAs lattice constant (5.65Å). Our calculations give a valence band off-set of $`\mathrm{\Delta }`$=0.405 eV ($`\mathrm{\Delta }`$=0.403 eV if the total DFT potential is considered instead of the electrostatic one). This value for $`\mathrm{\Delta }`$ is in very good agreement with both experimental results galexp  and early DFT calculations galthe . The resulting GaAs/AlAs band alignment is shown in figure 12; it provides an additional confinement potential for holes in the GaAs region. Therefore a stronger ferromagnetic coupling is expected.

### V.2 Electronic Structure

Also in this case the band structure and the DFT potential are the main quantities to investigate. First we study the evolution of the electronic properties as a function of the AlAs fraction of the superlattice. We construct GaAs(5-n)/2/AlAsn/GaAs(5-n)/2/(Ga,Mn)As1 superlattices, where the labels indicate the number of monolayers of the specific semiconductor. Note that the total number of monolayers in our supercell is six, and that the AlAs fraction is always located in the middle of the cell.

In figure 13 we present the band structure of a 50% DFH with Mn ions uniformly distributed in the plane (configuration FM1), for the cases $`n`$=0,1,3,5. As usual we consider only the in plane directions.

From figure 13 we can see that the only appreciable change in the band structure as the AlAs fraction increases is an enhancement of the band gap. This of course reflects the different AlAs/GaAs ratios of the superlattices and the larger bandgap of AlAs compared with GaAs (our LDA values are 1.7 eV and 0.6 eV respectively). For all the superlattices studied the magnetic moment of the unit cell is 16 $`\mu _\mathrm{B}`$ and the Mülliken analysis gives a Mn $`d`$ occupation of $``$4.7 and $``$0.8 respectively for majority and minority spins. Such an occupation is independent of the AlAs fraction and suggests that Mn is always in a $`d^5`$ state plus an antiferromagnetically coupled hole, as in the case of GaAs/(Ga,Mn)As DFH.

A closer look at the band structure reveals another important feature. The spin splitting of the valence band top, $`\mathrm{\Delta }_v=E_v^{}E_v^{}`$, is a non-monotonic function of the AlAs fraction, with values of 0.88 eV, 0.93 eV, 1.02 eV, and 0.96 eV for $`n=`$0, 1, 3 and 5 respectively. The initial increase is due to the enhanced confinement of the free holes in the Mn region. In fact the mean field expression for the valence band top spin splitting is simply Dietl ; usprb

$$\mathrm{\Delta }_v=xN\beta S,$$
(11)
where $`N\beta `$ is the $`p`$-$`d`$ exchange constant, $`S`$ is the mean spin ($`S`$=5/2 for (Ga,Mn)As) and $`x`$ is the Mn concentration. The exchange constant, $`N\beta `$, depends on the degree of overlap between the hole density and the Mn ions, and this is enhanced by hole confinement. Therefore we expect an increase of $`\mathrm{\Delta }_v`$ when the AlAs fraction is increased. The case $`n=5`$ is different, since no GaAs region is left and the additional confinement of the hole in the Mn plane due to the AlAs/GaAs valence band offset is partially lost.

Another important quantity to investigate is the DFT total potential. In figure 14 we present the macroscopic average along the superlattice direction of the DFT and Hartree potentials, and the electronic charge density, for a 50% DFH (configuration FM1), where we introduce three AlAs monolayers (GaAs1/AlAs3/GaAs1/(Ga,Mn)As1).

The figure shows that there is a large well for both majority and minority spin electrons in the AlAs region. This is mainly due to the Hartree component of the DFT potential and it is not spin sensitive. The width of this region depends on the thickness of the AlAs layer and plots for other values of $`n`$ give similar results. If we interpret the macroscopic average of the DFT potential in the spirit of the envelope function approximation, we can conclude that new electrons coming from intrinsic donors will be preferentially localized in the AlAs region. Therefore the ferromagnetism in AlAs/(Ga,Mn)As DFH appears to be more robust against electron doping than that in GaAs/(Ga,Mn)As DFH. This is consistent with the rather large $`T_C`$ found in AlAs/GaAs/(Ga,Mn)As DFH Tanaka ; Furdyna .

### V.3 Fit to the Heisenberg Model

As in the case of (Ga,Mn)As/GaAs DFH we investigate the strength of the ferromagnetic coupling by fitting our total energy calculation to third nearest neighbor Heisenberg model. We consider only the case of 50% Mn in the plane and we study the dependence of the coupling constants on the number of AlAs layers in the supercell. The results of our fit are shown in table 3.

From the table one can conclude that the total strength of the coupling, which is proportional to $`T_C`$, increases as a function of the AlAs fraction. This is consistent with an enhanced ferromagnetic coupling between the holes and the Mn ions due to confinement. Therefore in the absence of intrinsic defects, AlAs/(Ga,Mn)As DFH are more promising than GaAs/(Ga,Mn)As DFH as high $`T_C`$ DMS. It is also interesting to note that the different exchange constants behave in a different way when the AlAs fraction is increased: $`J_1`$ and $`J_3`$ are enhanced and $`J_2`$ is reduced. This behavior is not surprising within a carrier mediated ferromagnetism model (e.g. RKKY), since an increase of the AlAs fraction changes the value of the Fermi wave vector, and therefore the period of the exchange coupling.

Having established that defect-free AlAs/(Ga,Mn)As DFH present higher $`T_C`$ than their GaAs/(Ga,Mn)As counterparts, we finally investigate the stability of the ferromagnetic coupling against the presence of As antisites. As usual we introduce one AsGa per unit cell at various positions along the superlattice direction. Here we consider two limiting cases: 1) $`n=3`$ and the As antisite is located in one of the GaAs planes adjacent to the Mn plane, 2) $`n=5`$ and the As antisite is located in the middle of the unit cell (in the AlAs region).

In the first case, we find the coupling constants to be $`J_1=7.0`$ meV, $`J_2=0.0`$ meV, $`J_3=2.9`$ meV, $`x_iJ_i=4.95`$ meV. This is a considerable reduction of the ferromagnetic coupling with respect to the defect-free case. In this case the values of the coupling constants are almost identical to those of GaAs/(Ga,Mn)As DFH in which an antisite is introduced at the same position (in figure 11 the AsGa position is 1/6). Therefore, if the As antisites are introduced in the GaAs region, there will be no beneficial effects from the AlAs/GaAs band alignment.

The situation is rather different in the second case where the As antisites are introduced in the AlAs layer. Now the coupling constants are $`J_1=10.1`$ meV, $`J_2=0.1`$ meV, $`J_3=4.4`$ meV, and the reduction of the total coupling $`x_iJ_i`$ with respect to the defect-free case is only of about 30%. Interestingly, $`J_2`$ now assumes a negative value, suggesting some possible frustration even at low temperature.

In conclusion, AlAs/GaAs/(Ga,Mn)As DFH have stronger ferromagnetic interaction between the Mn ions than GaAs/(Ga,Mn)As DFH. Moreover, in the case that intrinsic defects are kept into the AlAs region, the ferromagnetic order is more robust against hole compensation.

## VI Conclusions

We have performed an extensive theoretical study of the electronic, magnetic and transport properties of GaAs/(Ga,Mn)As and AlAs/GaAs/(Ga,Mn)As DFH, using DFT within LSDA.

We find that GaAs/(Ga,Mn)As DFH show an half-metal band structure with metallic conductance in the Mn plane. The macroscopic average of the DFT potential indicates a selective confinement of the spin holes in the Mn planes and the Mn-Mn ferromagnetic interaction is non-monotonically dependent on the Mn concentration.

When compensating defects such as As antisites are introduced, the half-metallic state is lost and conducting channels appear in the minority spin band. These are due to hopping conductance through localized AsGa states. However, at least when the As antisites are far from the Mn planes, there is a spatial separation of the two spin currents with a metallic majority spin current located in the Mn planes, and an hopping-type minority spin current located primarily in the GaAs region. These differences in the type of transport for the two spin bands are magnified in the diffusive limit, for which we calculate a spin polarization of about 80%. Finally, the presence of As antisites generally weakens the ferromagnetic interaction, and local antiferromagnetic coupling between Mn ions is possible at low temperature.

With all these results in hand we conclude that GaAs/(Ga,Mn)As DFH behave as dirty planar metals, where the strength of the ferromagnetic coupling depends strongly on the amount and the position of the intrinsic defects.

Finally we have investigated the effect of additional confinement by studying AlAs/GaAs/(Ga,Mn)As DFH. In this case our accurate total energy calculations confirm that the band offset between GaAs and AlAs strongly confines the holes in the Mn region resulting in a larger Mn-Mn coupling. In addition we find that these structures are less sensitive to the presence of As antisites than the simpler GaAs/(Ga,Mn)As DFH.

We therefore conclude that band engineering, selective doping and the ability to control the actual position of As antisites or other compensating defects are the main keys to obtain room temperature ferromagnetism in DFH.

## Acknowledgments

This work is supported by Enterprise Ireland under the grant EI-Sc/2002-10. The calculations have been carried out using the computational facilities of the Trinity Centre for High Performance Computing (TCHPC). Useful discussions with N.A. Spaldin, and J.M.D. Coey are kindly acknowledged.


text:
# Nature of Charge Carriers in Disordered Organic Molecular Semiconductors

## Abstract

Understanding the charge carrier transport in the disordered organic molecular semiconductors is a fascinating and still unresolved problem in modern condensed-matter physics, yet has an extremely important bearing on their application in “plastic” based field effect transistor, light emitting diodes and lasers. The most contentious issue in this subject is the nature of the charge carriers i.e. whether they are bare electrons or dressed electrons, known as polarons. Here we show for the first time, by means of simple experiments that polaron moving in static disorder is responsible for charge carrier transport in disordered molecular semiconductors.

Since the discovery of “plastic” based transistorfg94 ; zb96  and light emitting devicescwt87 ; jhb90 ; nt96 , disordered molecular semiconductors are being widely investigated. These materials are composed of different types organic molecules starting from very small molecules to very large biomolecules like proteins and DNA, held together loosely by weak van der Waals type intermolecular force. The absence of long range order in these materials leads to the localization of the electronic wave function and results transport of charge carrier via thermally activated hops with carrier mobility $`\mu `$ as a strong function of temperature and electric field $`F`$ following a universallydhd96  observed Poole-Frenkel(PF) behavior $`\mu (F,T)=\mu (0,T)\mathrm{exp}(\gamma \sqrt{F})`$, where $`\mu (0,T)`$ is the temperature dependent zero field mobility and $`\gamma `$ is field activation of the mobility and recently, in light of theoretical studiessvn98 ; pep02 ; zgy00  we have shownakm03  another important feature i.e. (iv) charge carriers are spatially correlated in these materials. Considerable debate is going on the fundamental question like, what is the nature of charge carriers in disordered molecular semiconductors? Answer to this question will be a key input for understanding the charge transport mechanism and the development of new materials and new devices based on these materials. An indication of the difficulty in finding the nature of charge carriers and understanding the transport processes in these materials is evidenced by the conflicting viewpoints. At present, there are three viewpoints on the nature of charge carriers, which are (i) dressed electrons(known as polarons) due to strong electron-phonon interaction and the temperature dependence of the $`\mu `$ arises due to polaron binding energylbs90 ; (ii) bare electrons and temperature dependence of $`\mu `$ is due to energetic and spatial disorderpmb91  and (iii) third viewpointpep02 ; zgs00  is the combination of these two opposite viewpoints and the charge carriers are polarons moving in disorder and the temperature dependence of $`\mu `$ is due to both static disorder and polaron binding energy. It has been shownpep02 ; lbs90  that polaron based models results unacceptable values of polaron binding energy and strong nearest neighbor intermolecular coupling if disorder is not included. As mentioned earlier, the intermolecular coupling in these disordered molecular materials is very weak and can’t account for strong nearest neighbor coupling. If it is assumed that energetic and spatial disorder are responsible for thermal activation of $`\mu `$ and bare electrons, not polarons, are responsible for charge carrier transport, the probability of hopping is drastically reduced and again unreasonably strong intermolecular coupling is required to explain the experimental data. Here, we show that there is a natural solution to this apparent paradox and polaron is the nature of charge carriers, emphasizing the important role of both disorder and electron-phonon interaction on the charge carrier transport in these disordered materials.

We have chosen one of the most importantzb96 ; gp98  molecular solid based on Copper phthalocyanine(CuPc) molecules because of their high chemical stability and ease to prepare the devices. Details about the CuPc-based single layer devices are given in Ref.akm02 . Here, we report the experimental investigation on charge carrier transport in hole only devices based on metal/CuPc/metal structures. In this case, by properly choosing contacting metals, current injection and transport due to holes have been investigated. Fig.1 shows the temperature dependent current-voltage(J-V) characteristics in ITO/CuPc/Al structure. At low bias, J-V characteristic follow the slope of two in log(J)-log(V) plot, but as the bias increases the slope increases gradually to higher value due to space charge limited transport processakm01 , because the ionization potential of MePc(4.8eV)gp98  is close to the work function of ITO(4.75eV). A numerical workoutakm01  has been used by solving Poission’s equation $`dF(x)/dx=ep(x)/ϵ`$, current density relation $`J(x)=ep(x)\mu (x)F(x)`$ and the PF relation of carrier mobility $`\mu (F,T)=\mu (0,T)\mathrm{exp}(\gamma \sqrt{F})`$, simultaneously. Here, $`ϵ`$ is the dielectric constant of CuPc and $`p(x)`$ is the hole density at position $`x`$ and the boundary condition is takenakm02 ; akm01  at the ITO/CuPc interface. The simulated results are shown as solid lines in Fig.1 at different temperatures. Inset of Fig.1 shows the temperature dependence of conductivity $`\sigma (T)`$ for CuPc. Linear dependence of $`ln(\sigma )`$ on $`1/T^{1/4}`$ validates the variable range hoppingnfm79 , $`\sigma (T)=\sigma _0exp\{(T_0/T)^{1/4}\}`$, where $`\sigma _0`$ is the temperature independent conductivity and $`T_0`$ is the characteristic temperature. Hence the excellent agreement of the simulated results with experimental data presented in Fig.1 establish the carrier transport process, which is thermally activated hopping with field dependent mobility.

There are basically three models to explain the charge carrier transport in these materials. In a very first approach, Gillwdg72  attempted to describe the universally observed thermally activated and PF behavior of $`\mu `$ using a phenomenological non-Gaussian disorder model(NGDM), $`\mu (T,F0)\mathrm{exp}(\mathrm{\Delta }/k_BT)`$, where $`\mathrm{\Delta }`$ is the temperature independent activation energy. This model has been criticizedsvn98 ; akm03 ; hb93  for lacking a first principle explanation of PF behavior of $`\mu `$ and non-inclusion of another universal feature i.e. the Gaussian distribution of energy levels, $`g(E)\mathrm{exp}(E^2/4\sigma ^2)`$, where $`\sigma `$ is the r.m.s deviation of hopping site energies. Bassler proposedhb93  the uncorrelated Gaussian disorder model(UGDM), which describes the carrier transport as a biased random walk among the dopant molecules with Gaussian-distributed random site energies due to positional and energetic disorder. Although UGDM explains some features of experimental data and provides support for PF behavior of carrier mobility, several discrepanciesakm03  emerge with uncorrelated description of Gaussian disorder model. Garstein and Conwellyng95  first showed that a spatially correlated potential is required for the description of PF behavior of mobility and subsequently Novikov et al.svn98  have proposed a correlated Gaussian disorder model(CGDM) to describe the charge carrier transport in these materials. Recently, we have shownakm03  that the CGDM successfully explains the experimental data emphasizing, whatever be the nature of charge carriers, charge transport occurs by correlated hopping among the molecular sites distributed in Gaussian density of states(GDOS) of highest occupied molecular orbital(HOMO) and/or lowest unoccupied molecular orbital(LUMO) in these disordered materials. In case of both Gaussian disorder models, the temperature dependence of zero field mobility is given by $`\mu (T,F0)\mathrm{exp}(A\sigma ^2/k_B^2T^2)`$, where $`A`$ is $`2/3`$ in UGDMhb93  and $`3/5`$ in CGDMsvn98 . The Aerrhenious plots result an apparent activation energy $`E_c`$, which is $`E_c=k_B\{d(ln\mu )/d(1/T)\}=\mathrm{\Delta }`$ in NGDMwdg72  and $`B\sigma ^2/k_BT`$, in case of Gaussian disorder models and $`B`$ is $`8/9k_B`$ in UGDMhb93  and $`18/25k_B`$ in CGDMsvn98 . If we take the contributions both from the polaron binding energy $`E_{pol}`$, and from the static disorder $`E_{dis}`$, $`E_c`$ should be $`E_c=E_{pol}+E_{dis}`$. Fig.2 shows the temperature dependence of zero field mobility and it is clear that both $`ln(\mu )`$ vs. $`1/T`$ and $`ln(\mu )`$ vs. $`1/T^2`$ result nonlinear Arrehenious plots and it is impossible to distinguish between $`E_{pol}`$ and $`E_{dis}`$ and their respective values from $`E_c`$. Here, we show that the interplay between these two contributions on the carrier transport can be explored by studying the temperature dependence of $`\mu `$ over extended range of temperature and measuring atleast one contribution in Ec, independently. It is clear from Fig.2 that both, NGDM and UGDM or CGDM agree well with experimental data in higher temperature region($`T140K`$) and gradual change in slope in the Arrehenious plots can be explained either by invoking the distribution of $`E_c`$, or by distribution of $`\sigma `$, but the underlying assumption behind the second proposition is hard to justify. We have found that the Gaussian distribution of $`E_c`$ i.e. $`\varphi (E_c)=\mathrm{exp}[(E_cE_{c0})^2/4\sigma _c^2]`$ and $`\mu (0,T)=\mu _0_0^{\mathrm{}}\varphi (E_c)\mathrm{exp}(E_c/k_BT)𝑑E_c`$ explain the data excellently(shown in Fig.3). $`E_{c0}`$, which is the maximum activation energy and $`\sigma _c`$, are the center and width of the Gaussian distribution and found to be 540meV and 80meV, respectively. In this case, the temperature dependence of mobility follows $`ln(\mu )1/k_BT`$ instead of $`ln(\mu )1/(k_BT)^2`$ according to CGDMsvn98 . The spatial correlation in CGDMsvn98  has been shown to be resulted from the long-range interaction between charge carriers and permanent dipole moments of doped molecules in polymers and/or host molecules. However, it has been pointed outzgy00  that the mechanism responsible for PF behavior in different conjugated polymers and molecules cannot be due to charge-dipole interaction, because the PF behavior of $`\mu `$ has been universally observed in several doped and undoped organic semiconductors based on polymers or molecules with or without dipole moment. Recently, Yu et. al.zgy00  have shown using first principle quantum chemical calculation that the thermal fluctuations in the molecular geometry can lead to spatial correlation through intermolecular restoring force and different temperature dependence in this case arises due to the fact that energetic disorder is temperature independent in CGDM, whereas it increases with temperature in molecular geometry fluctuation modelzgy00 ; zgy01  resulting $`ln(\mu )1/k_BT`$ temperature dependence. We have used highly symmetric molecules with negligible dipole moment for our investigations and we find it hard to justify strong long-range charge-dipole interaction to be the origin of spatial correlation.

Fig.4 shows the absorption spectra of CuPc. The characteristic two-humped spectra are known as Q-band(14) in CuPc. The absorption co-efficient $`\alpha (E)`$ for a given photon energy E is proportional to the probability $`P_{if}`$ for the transition from initial state $`i`$(in HOMO) to the final state $`f`$(in LUMO) and the density of the initial and final state and given by, $`\alpha (E)\mathrm{\Sigma }P_{if}`$$`\rho `$i$`\rho `$f, where $`\rho `$i and $`\rho `$f are the density of states in HOMO and LUMO of CuPc, respectively. There are two important parameters involved in the absorption spectra. First is the center of the peak at around 2eV, which is the energetic separation between maxima of HOMO and LUMO and second is the full width at half maximum of about 460meV, which should be the maximum energetic separation between two hopping sites within the intrinsic GDOS, as shown schematically in Fig.4. Hence, the maximum contribution in the activation energy from static disorder will be around 460meV. We have also found that the 540meV is the maximum activation energy($`E_{c0}`$), which has both contributions from static disorder and polaron binding energy. Combining these two electrical and optical measurements, we found 80 meV(=540-460meV) is the polaron binding energy. If we include the lower and upper limits of activation energy due to static disorder, which are 500meV and 580meV respectively, the polaron binding energy varies between 40 to 120meV. These observations are consistent with the third viewpoint i.e. disordered polaron moving in a correlated energy landscape is responsible for charge transport in disordered organic molecular semiconductors. These experimental findings settle an extremely important issue regarding the nature of charge carriers and have shown conclusively that polarons moving among static disorders are responsible for charge carrier transport in disorder molecular semiconductors.

Figure captions

J-V characteristics of 100nm CuPc based single layer device with ITO cathode contact and Al anode contact at different temperatures starting at 300K and then at the interval of 30K. Experimental data are shown by the symbols and solid lines represent the simulated data. Inset shows the log of conductivity of CuPc vs. 1/T1/4. Empty circles are experimental data and solid line is fit with straight line.

Temperature dependence of zero field mobility against $`1/T`$(a) and $`1/T^2`$(b). Solid lines are linear fit to data, which results in (a) $`\mu _0=2\times 20^4cm^2/Vsec,\mathrm{\Delta }=450meV`$ and in (b) $`\mu _0=2\times 10^8cm^2/Vsec,\sigma =85meV`$.

Theoretical fit to temperature dependence of zero field mobility in CuPc for two different thicknesses using Gaussian distribution of activation energy, which is shown in inset.

Absorption spectra of Cu-Pc for two different thicknesses at room temperature. The spectral characteristics and width of the spectra do not depend on the thickness of the sample. Inset shows the hopping sites and hopping processes inside the intrinsic density of states of disordered molecular semiconductors.