# Silicon nanoparticles and interstellar extinction

## 1. Introduction

Recently, extended red emission (ERE) has been detected in the diffuse galactic background and in high-galactic latitude cirrus clouds with surprisingly high intensities (Gordon, Witt, & Friedmann 1998; Szomoru & Guhathakurta (1998)). This emission, appearing in the 500–800 nm spectral range as an unstructured broad feature, is attributed to photoluminescence by some component of interstellar grains. The correlation between the ERE R-band intensity and H I-column density of (1.43$`\pm `$0.31) 10<sup>-29</sup> ergs s<sup>-1</sup> Å<sup>-1</sup> sr<sup>-1</sup> H atom<sup>-1</sup> (Gordon et al. (1998)) implies that, at a minimum, (10$`\pm `$3)% of all UV/visible photons in the diffuse interstellar radiation field are absorbed by the ERE producing grains, if each absorption results in the emission of an ERE photon. This requires that the ERE-grains make a significant contribution to the interstellar extinction in the UV/visible range, which further implies that they must consist of cosmically abundant elemental constituents in a form that permits extremely high efficiency photoluminescence.

After a review of possible ERE-grain candidates, Witt, Gordon, & Furton (1998) and Ledoux et al. (1998) independently proposed that silicon nanoparticles (SNPs) might be the source of ERE in the interstellar medium in as far as they produce photoluminescence spectra closely matching those observed in ERE sources and match the constraints regarding the required quantum efficiency and elemental abundance. It was discovered experimentally that the photoluminescence emission originates from nanocrystalline Si regions in porous Si material (Canham (1990); Cole et al. (1992)) and from clusters of nanosized grains (Takagi et al. (1990); Littau et al. (1994); Tamir & Berger (1996)). The estimate of the amount of silicon needed in the form of SNPs, however, was based upon the average UV absorption cross section of crystalline silicon in bulk form. This must be considered as only a rough approximation, because the remarkable optical properties of SNPs, clusters involving a few 10<sup>2</sup> silicon atoms each with a silicon suboxide (SiO<sub>x</sub>) surface covering, arise precisely because quantum confinement alters the band structure of the cluster material relative to that in the bulk material. Since quantum confinement is a function of cluster size, so are the resulting photoluminescence characteristics, and so are the dielectric functions of the cluster material.

The current investigation was undertaken to answer several related questions: What are the UV/optical extinction characteristics of a separate component of SNPs? What fraction of the silicon believed to be depleted into solid grains is needed in the form of SNPs to explain the observed ERE intensities? What resulting characteristics of the interstellar extinction curve can be related to absorption by SNPs and can thus be correlated with varying ERE intensities? To find answers on these questions, we made use of a powerful computational approach based on the method of regularization (Zubko (1997)), which was proven to be efficient in modeling of interstellar dust (Zubko, Krełowski, & Wegner 1996, 1998).

## 2. Optical properties of Si nanoparticles

The first step in our study was to choose the optical constants of SNPs. Witt et al. (1998) proposed that the interstellar SNPs should have diameters of 1.5–5 nm because only grains in this size range exhibit efficient photoluminescence. Evidently, the dielectric properties of such SNPs should be different from those of a bulk material because of both the quantum size confinement effect and the increased role of surface states. These expectations are fully confirmed by available experimental data (Koshida et al. (1993); Theiß (1997)). In particular, Theiß (1997) reported the dielectric function of nanosized silicon from porous samples with a range of porosities 60–80%, corresponding to the respective range of crystallite sizes of 5–2 nm. These results show that the optical properties of silicon nanostructures have a strong size dependence. However, an accurate derivation of the latter is not a trivial problem, because in each silicon sample there is some size distribution of crystallites (Theiß (1997)). Note that Theiß’ (1997) dielectric function covers the wavelengths 0.2–1 $`\mu `$m only. However, as we will see below, we especially need the data down to the Lyman limit (912 Å). We therefore decided to use in our modeling the optical constants of nanosized silicon by Koshida et al. (1993) spanning the range 0.055–0.85 $`\mu `$m, which is sufficient for our problem. These constants correspond to the characteristic diameter of a SNP of around 3 nm. The optical constants of nanosized silicon by Koshida et al. (1993) and of bulk silicon taken from the compilation by Palik (1991) are displayed in Fig. Silicon nanoparticles and interstellar extinction. There is a considerable difference between the two sets which may also be seen in the extinction efficiencies of the respective spherical grains shown in Fig. Silicon nanoparticles and interstellar extinction. The first three cases correspond to the SNPs used in our modeling (see Section 3 for more details). Curves 3 and 4 demonstrate the so-called extrinsic size effect for small particles when the bulk optical constants are used. The peak at 0.118 $`\mu `$m is due to the SiO<sub>2</sub> shell and is present also in the spectra of bulk material, whereas the peaks at 0.153 $`\mu `$m and 0.138 $`\mu `$m (for 3 and 4, respectively) are surface plasmons due to the silicon core, specific for small particles. The peak position depends on the volume fraction of Si. In contrast to the latter cases, curve 1 shows the intrinsic size effect when the optical constants themselves vary with grain size. Note that Draine & Lee (1984) already computed the size-dependent dielectric function of small graphite grains. However, the size dependence was taken into account in their calculation only for the free-carrier part of the dielectric function, whereas the part due to the interband transitions was set to be the same as for bulk graphite. In contrast to Draine & Lee (1984), the optical constants of nanosized silicon used in the present study explicitly reflect the drastic changes in the band structure and interband transitions of the SNPs in comparison with those of bulk silicon.

## 3. Interstellar extinction with Si nanoparticles

The dust models investigated for the present study were expected to satisfy three independent constraints simultaneously: 1) fit the mean Galactic extinction curve as closely as possible over the entire near-IR to far-UV range; 2) consume depleted heavy elements consistent with the recently proposed reference abundances for the interstellar medium (about 2/3 of solar values, see e.g., Snow & Witt 1996); and 3) require the ERE-producing SNPs to absorb at least 0.10$`\pm `$0.03 of the UV/visible photons in the interstellar radiation field, as suggested by the observations of Gordon et al. (1998). The problem was solved by using the approach and computer program based on the method of regularization (Zubko (1997); Zubko et al. (1998)) which allows one to find the size distributions of the dust components in the most general form. The size distributions may be subject to the cosmic abundance and mass fraction constraints. Following Zubko et al. (1998), we treated the mixtures of spherical bare, multilayer and/or composite grains, whose extinction efficiencies were calculated either with the standard Mie theory for bare and composite grains (Bohren & Huffman 1983) or with its extension to multilayer particles. For composite grains the effective dielectric function was first calculated using the effective medium approach by Stognienko, Henning, & Ossenkopf (1995).

The fraction of UV/visible photons absorbed by SNPs, $`\beta `$, was calculated with the formula

$$\beta =\frac{_{0.0912\mu m}^{0.55\mu m}(1a_\lambda ^{\mathrm{SNP}})\tau _\lambda ^{\mathrm{SNP}}I_\lambda ^{\mathrm{ISRF}}d\lambda }{_{0.0912\mu m}^{0.55\mu m}(1a_\lambda )\tau _\lambda I_\lambda ^{\mathrm{ISRF}}d\lambda }$$
(1)   
where $`a_\lambda `$ ($`a_\lambda ^{\mathrm{SNP}}`$) is the albedo of the entire dust mixture (SNPs), $`\tau _\lambda `$ ($`\tau _\lambda ^{\mathrm{SNP}}`$) is the extinction of the entire dust mixture (SNPs), $`I_\lambda ^{\mathrm{ISRF}}`$ is the intensity of the interstellar radiation field at the Earth in units of photons cm<sup>-2</sup> s<sup>-1</sup> Å<sup>-1</sup>. The $`a_\lambda `$ was taken from Gordon et al. (1998), $`\tau _\lambda `$, the mean Galactic extinction ($`R_V`$=3.1) from Cardelli, Clayton, & Mathis (1989) and $`I_\lambda ^{\mathrm{ISRF}}`$ from Mathis, Mezger, & Panagia (1983). The values of $`a_\lambda ^{\mathrm{SNP}}`$ and $`\tau _\lambda ^{\mathrm{SNP}}`$ were taken from the models.

We based our calculations on the G, M and O types of models introduced by Zubko et al. (1998). A G model contains the constituents usual for Greenberg’s models: the bare graphite grains and the silicate core–organic refractory grains (e.g. Li & Greenberg 1997). An M model is a mixture of the bare graphite and silicate grains together with the porous composite grains, resembling recent Mathis’ (1996) models. The constituents of an O model are the bare graphite and silicate grains together with the multilayer grains consisting of a silicate core coated by refractory organic and water-ice shells.

Initially, we tried to model the extinction using the above models to which we added SNPs of 3.0 nm diameter covered by a SiO<sub>2</sub> mantle. We varied the thickness of the mantle and found that the best results were achieved when the mantle is quite thin. However, all the models resulted in quite low $`\beta `$, as a rule not exceeding 0.03–0.04, and, as a rule, consumed the solar fractional amount of silicon, 35 ppm (atoms per 10<sup>6</sup> H atoms). For the next step we introduced spherical porous clusters of SNPs instead of isolated SNPs. This resulted in an increase of $`\beta `$, typically by 0.003–0.005 (the highest values correspond to 70% porosity). Then we tried combining the G, M, and O models and found that the only mixture that results in acceptable $`\beta `$ ($`>`$ 0.07) is a combination of G and O models or the GO model. It consists of four components: bare graphite grains, silicate core-organic refractory mantle grains, three-layer silicate-water ice-organic refractory grains and, finally, the SNPs in the form of either silicon core-SiO<sub>2</sub> mantle grains or 70%-porous aggregates of silicon grains containing a small amount of SiO<sub>2</sub>. The GO model requires a mass fraction of 7% of silicon grains. It results in $`\beta `$=0.071 and 0.081 for the models with isolated and clustered SNPs, respectively. Note, however, that these models still consume much carbon, 190 ppm, and a solar fractional amount of silicon. The GO model seems more natural than G and O models separately, because when the dust grains in the interstellar medium do evolve through the formation and processing of mantles, we should expect the contributions into extinction of various intermediate stages.

The main results of our calculations are presented in Fig. Silicon nanoparticles and interstellar extinction and Tables 12. First of all, we see that the models with bulk silicon exhibit rather strong features in the UV (see Fig. Silicon nanoparticles and interstellar extinction) which so far have not been observed. For this case we adopted the volume fractions: $`\delta _{\mathrm{Si}}`$=0.297 and $`\delta _{\mathrm{SiO}_2}`$=0.703 corresponding to the initial assumption of Witt el al. (1998) about an equal amount of silicon and oxygen atoms in a SNPs. By contrast, the contribution of the SNPs to the extinction is featureless when the optical constants of nanosized silicon and a very thin SiO<sub>2</sub> mantle are used. As a result, such models fit the mean Galactic extinction much better. Practically all of the models require much carbon: 180–190 ppm, except O models for which C/H=100 ppm, which is about optimal. As found in previous models by Zubko et al. (1998), more oxygen is needed for the O models. The amount of silicon needed requires solar relative abundances. A remarkable feature of the GO models in contrast to the other models is the extremely small amount of magnesium and iron consumed, about 17 ppm, which is quite close to the respective optimum values by Snow & Witt (1996). In addition to providing the highest $`\beta `$ values, the GO models also show the closest fit to the observed mean Galactic extinction curve.

A result found to be generally true for all of our models is that $`\beta `$ is approximately equal to the mass fraction incorporated in the SNPs (see Table 2). This result is largely independent of whether the SNPs are included as a single-size component of $`a`$=1.5 nm, an $`a^3`$ distribution of porous SNP clusters in the range 1.5–50 nm, or, as pointed out by the referee, if SNPs are included as the small-size tail of an $`a^{3.5}`$ distribution, as long as their mass remains constant. Since the cosmic abundance of Si limits this mass fraction severely and approximately 50% of the available Si is already incorporated in the SNPs in the GO models, one important conclusion to draw is that if ERE is produced by SNPs, the intrinsic photon conversion efficiency must be extremely high, essentially near 100%.

One reason why the $`\beta `$ values from Table 2 are as small as they are is that the number of photons in the assumed radiation field is highest in the 0.35–0.55 $`\mu `$m wavelength range, where the absorption contribution of the SNPs is practically zero. One would obtain larger values of $`\beta `$, if the interstellar radiation field contained increased numbers of UV photons. If one can make a case for significant differences in the spectral energy distribution of the interstellar radiation field in different regions of the Galaxy, one should be able to predict corresponding variations in the relative brightness of the ERE and the visible diffuse galactic light (DGL). Such variations should be apparent in results from ongoing surveys which map the DGL and the ERE over a wide range of galactic longitudes (e.g., Gordon et al. (1998)).

We conclude that in general the results of our models are consistent with the hypothesis that SNPs are the source of ERE in the interstellar medium. Their extinction contribution occurs primarily at wavelengths shorter than 300 nm and is not expected to introduce discernable structure into the interstellar extinction curve, provided one takes into account the size dependence of the optical constants for nanostructured silicon. The intrinsic photon conversion efficiency of such SNPs must be near 100%, if cosmic abundance constraints are to be met. Spherical clusters of SNPs with cluster radii up to 50 nm provide a slightly better match to the ERE requirement than do single SNPs with the same total mass fraction. It would be of great interest to predict possible spectral features due to SNPs in the infrared, as well as the contribution of SNPs in the total thermal emission of interstellar dust. However, we cannot do this because of the lack of optical constants of SNPs in the infrared and because of lacking information about the size distribution of SNPs.

We thank Prof. N. Koshida for providing us the electronic table of the optical constants of nanosized silicon.