# The SiC problem: astronomical and meteoritic evidence

## 1 Introduction

Most of the solid material in the solar system is believed to have originated as small particles that condensed in outflows from stars. However, most solar system solids (predominantly silicates) have been reprocessed and/or homogenized so extensively that even the most primitive meteorite silicate samples no longer contain evidence of their origins. But some types of dust particles in the solar system have not been reprocessed and can potentially be associated with their stellar origin. One such dust type, silicon carbide (SiC), is believed to be a significant constituent of the dust around carbon-rich AGB stars (Gilman 1969; Treffers & Cohen 1974). Silicon carbide grains can be divided into two basic groups: $`\alpha `$-SiC if the structure is one of the many hexagonal or rhombohedral polytypes and $`\beta `$-SiC if the structure is cubic (e.g., Bechstedt et al. 1997). Silicon carbide grains exhibit a strong mid-infrared feature between 10 and 12 $`\mu `$m, with the peak of the $`\beta `$-SiC feature occurring about 0.4 $`\mu `$m shortwards of that for $`\alpha `$-SiC. Until now, the observed peak wavelengths of the SiC feature in astronomical spectra have been interpreted as indicating $`\alpha `$-SiC to be the dominant type of SiC around carbon stars (e.g. Baron et al. 1985; Pégourié 1988; Groenewegen 1995; Speck et al. 1997a,b). In fact, Speck et al. 1997a,b found no evidence of $`\beta `$-SiC in these circumstellar environments. Silicon carbide grains found in meteorites have isotopic compositions which imply that most of these grains were formed around carbon stars, with small amounts forming around novae and supernovae (see Hoppe & Ott 1997; Ott 1993 and references therein). All studies to date of meteoritic SiC grains have found them to be of the $`\beta `$-type (Bernatowicz 1997). $`\beta `$-SiC will transform into $`\alpha `$-SiC above 2100<sup>o</sup>C but the reverse process is thermodynamically unlikely. There is therefore an apparent discrepancy between the meteoritic and astronomical SiC-types, which has been discussed in detail by Speck et al. (1997a,b).

We present new infrared (IR) absorption measurements of thin films of $`\alpha `$\- and $`\beta `$-SiC created by compression in a diamond anvil cell. Unlike some other methods, a dispersive medium (such as potassium bromide; KBr) is not used. This relatively new approach is quantitative, if sufficient care is taken to produce an appropriately thin and uniform film, as shown by comparison of thin film spectra of various minerals to reflectivity data from the same samples (Hofmeister 1995; 1997 and references therein). Moreover, thin film spectra of garnets are nearly identical to single-crystal absorption data acquired in a vacuum (Hofmeister, 1995): hence, thin film spectra can be applied to astronomical data without further manipulation. Our measurements strongly suggest, through comparison of the new thin film data with previous IR spectra collected for fine-grained KBr dispersions (in which the dust particles are dispersed in a KBr pellet), that the “matrix correction” wavelength shift, invoked by Dorschner et al. (1978) and adopted by other authors (e.g. Friedemann et al. 1981; Borghesi et al. 1985), should not be applied to laboratory spectra of sub-micron grain size dispersions of SiC: it was the use of this “KBr correction” which caused the above-mentioned discrepancy between the SiC-types found in meteorites and around carbon stars. A companion paper (Hofmeister & Speck, in preparation) clarifies of the roles of scattering, absorption, reflection, and baseline correction in laboratory measurements, sheds light on problems associated with the powder dispersion technique, and discusses the conditions appropriate for the application of such data.

## 2 Laboratory techniques and results for thin-film samples

Single-crystals of $`\alpha `$-SiC were purchased from Alpha/Aesar (catalog no. 36224). This specimen is 99.8% SiC, consisting of hexagonal platelets of 50 to 250 $`\mu `$m in diameter and 5 to 15 $`\mu `$m thick. Less than 1% of the platelets had an amber color, the remainder were pale grey. All were transparent in the visible with smooth, highly reflective surfaces. Polycrystals of $`\beta `$-SiC were donated by Superior Graphite. The purity of this sample is also 99.8%. One batch consisted of 1 $`\mu `$m powder, the other was a conglomerate of equant crystallites of up to 25 $`\mu `$m in size. For this study, only the gray crystals of $`\alpha `$-SiC were examined.

Mid-IR spectra were obtained from 450 to 4000 cm<sup>-1</sup> (2.5-22.2 $`\mu `$m) at 2 cm<sup>-1</sup> ($``$ 0.01 $`\mu `$m) resolution using a liquid-nitrogen cooled HgCdTe detector, a KBr beam splitter and an evacuated Bomem DA 3.02 Fourier transform interferometer. Thin films were created through compression in a diamond anvil cell which was interfaced with the spectrometer using a beam condenser. Type II diamonds were used. Film thickness was estimated from the initial grain size, by the relative relief and color seen among the various films, and by the increase in grain diameter from the initial size during compression. Efforts were made to cover the entire diamond tip (0.6 mm diameter) with an even layer of sample, but slight irregularities in the thickness were inevitable. Reference spectra were collected from the empty DAC. Uncertainties in peak positions are related to peak widths because the accuracy of the FTIR spectrometer is high, $`\pm `$0.01 cm<sup>-1</sup>. For procedural details see Hofmeister (1997).

Spectra obtained from $`\alpha `$-SiC (Fig. 1a,b) have an intense, broad band near 11.8 $`\mu `$m. The peak position lies between the longitudinal optic mode (LO) and transverse optic mode (TO) components observed by Spitzer et al. (1959) and a shoulder is seen at the LO position. A shoulder also occurs at 12.2 $`\mu `$m. The sample thickness could not be precisely determined, but was estimated to be sub-micron. Spectra obtained from $`\beta `$-SiC (Fig. 1c-g) depend somewhat on thickness. For the thinnest films, of sub-micron thickness (Fig. 1c,d), a fairly symmetric peak is found at 11.3 to 11.4 $`\mu `$m, and a weak shoulder exists at 10.7 $`\mu `$m, consistent with excitation of the LO component. Spectra from thicker film samples, $``$$`\mu `$m in thickness from visual inspection (Fig. 1e,f), have a peak at a similar position, with an asymmetric increase in intensity on the short-wavelength side, and display additional weak features. The 12.7 $`\mu `$m band is due to the TO feature. The weak, broad band at 13.4 microns is not an absorbance feature but is due to the Christiansen effect which gives a minimum when the real part of the index of refraction is unity (Hapke 1993). The asymmetry of the main peak is due to the baseline rising towards the visible, probably a scattering effect from the grain boundaries. A spectrum from the thickest sample examined ($``$$`\mu `$m), has high absorbance values overall, with the Si-C stretching peak superimposed (Fig. 1g). The appearance of the peak is intermediate between the peaks observed from the thin (Fig. 1d) and moderately thick samples (Fig. 1e), in that the main peak is symmetric but a weak subsidiary feature exists at 12.7 $`\mu `$m. Below 8 $`\mu `$m, the absorbance in Fig. 1g drops, rather than increasing as in the other spectra, because of interference fringes in the near-IR (not shown). These interference fringes indicate a distance of 5 $`\mu `$m, inferred to be the separation of the diamond anvils. The peak positions of the $`\beta `$-SiC samples are relatively independent of the thickness. No difference can be discerned between the two samples of $`\beta `$-SiC (fine grain size vs. mixed grain sizes). Fig. 1c,g were made from a mixture of grain sizes and Fig. 1d,e,f are from the 1 $`\mu `$m powder fraction. Additional spectra from both $`\beta `$\- samples resembled those shown. The appearance of the spectra are consistent with being due to pure absorption for the thinnest samples (Fig. 1c,d) and absorption with minor reflection for the thicker samples (Fig. 1e-g), given that the LO-TO coupling is stronger in $`\beta `$-SiC than in $`\alpha `$-SiC (Hofmeister & Speck, in preparation).

## 3 Comparison with dispersed-sample results

KBr matrix spectra of $`\beta `$-SiC obtained by Borghesi et al. (1985) for a fine grain size sample (mean diameter modeled by them as 0.02 $`\mu `$m, average diameter observed in TEM as 0.12 $`\mu `$m) closely match our own thin-film data, particularly the spectrum in Fig. 1e (shown in Fig.2a). The greatest difference is that the TO mode appears as a shoulder, rather than a separate peak. This difference is obviously due to sample thickness, because the thinner film of Fig. 1d has a barely discernable shoulder at the TO position. The LO mode occurs as a weak shoulder in their dispersion data. Their uncorrected peak barycenter was at 11.4 $`\mu `$m, the same as for our thin films. The match of Borghesi et al.’s dispersion data with Fig. 1e is consistent with an estimated film thickness $`<`$0.1 $`\mu `$m. The $`\beta `$-SiC spectrum of Papoular et al. (1998), with maximum absorbance of 0.4, has a peak at 11.5 $`\mu `$m, in agreement with previous results and Fig. 1. Papoular et al. (1998) also present two unusual spectra of $`\beta `$-SiC consisting of broad overlapping peaks at 10.9 and 12.2 $`\mu `$m. These positions are close to the TO and LO components. The very high absorbance units of 1 and 2.5 for these samples suggest over-loaded pellets. For extreme concentrations of SiC (or large thicknesses), light is reflected between the TO and LO modes: the scattering in the pellet produces the dip in absorption. Problems occur at high absorption because the partial opacity induces a frequency dependent baseline.

For $`\alpha `$-SiC, the KBr-dispersion spectrum of Borghesi et al. (1985)’s smallest-grained (mean diameter modeled by them as 0.04 $`\mu `$m, average diameter observed in TEM as 0.16 $`\mu `$m) and purest sample (SiC-600) closely matches the spectrum of our thinnest film (Fig. 1a; comparison shown in Fig. 2b). Its peak position of 11.6 $`\mu `$m equals our result, given the experimental uncertainties. The positions of the shoulders are comparable to the LO and TO positions (Spitzer et al. 1959). Their sample N is compromised by $``$ 10% impurities (C and SiO<sub>2</sub>). Their SiC-1200 sample was 3-10 times larger grained, even for the ground and sedimented fraction, and is inappropriate for comparison. The study by Friedemann et al. (1981) involved larger grain sizes, but yielded similar spectral profiles, with a slight shift of the peak position to 11.8 $`\mu `$m.

It is clear that the introduction of a KBr matrix wavelength correction (e.g. Friedemann 1981) is incorrect, since the barycenter peak for KBr dispersions with fine grain sizes and reasonably low concentrations equals that of corresponding thin films, while the peak shapes are in excellent agreement. For these ($`<`$0.1 $`\mu `$m) grain sizes or film thicknesses, bulk absorption rather than surface effects dominates in the vicinity of the intense peak. Only for extremely thick or large grain samples, $``$$`\mu `$m, do the parameters of the dispersions differ from those of a bulk sample but the differences are due to internal scattering among the particulates and sample opacity leading to incorrect assumptions for zero transmission. This issue is discussed further by Hofmeister & Speck (in preparation). Similarly, the application of a KBr correction for silicates (Dorschner et al. 1978) is also problematic. Recent measurements by Colangeli et al. (1993, 1995) indicate minimal matrix effects for various silicates. Thin film data on the other hand do not suffer from these problems.

## 4 Implications for the SiC-type that best matches carbon star spectra

Having established that previous fits of laboratory spectra for SiC to astronomical spectra have been erroneous due to the unnecessary application of a KBr correction factor, we have re-fitted our own UKIRT CGS3 spectra of carbon stars (Speck et al. 1997a,b) without such a correction. We used the same $`\chi ^2`$–minimization routine described by Speck et al. (1997a,b) but the Borghesi et al. (1985) data for $`\alpha `$-SiC (SiC-1200, SiC-600 and SiC-N) and for $`\beta `$-SiC, to which Speck et al. (1997a,b) applied the usual KBr correction, were used uncorrected this time.

A detailed discussion of the fitting procedure can be found in Speck et al. (1997a). The routine was used on the flux-calibrated spectra, over the whole wavelength range (7.5–13.5 $`\mu `$m). All attempted fits involved either a blackbody or a blackbody modified by a $`\lambda ^1`$ emissivity, together with some form of silicon carbide. The results are listed in Table 1 and representative sample fits are shown in Fig. 3. The $`\chi _R^2`$ values are the reduced $`\chi ^2`$ values, given by dividing the $`\chi ^2`$ value by the number of degrees of freedom. The fitting routine was unable to find fits for four of the spectra, those of AFGL 341, AFGL 2699, V Aql and Y CVn. However, these four spectra are unusual in that they display a strong feature in the 7.5-9.5 $`\mu `$m region (see Fig. 2 of Speck et al. 1997a), possibly identifiable with $`\alpha `$:C–H hydrogenated amorphous carbon (Baron et al. 1987, Goebel et al. 1995), and need to be classified separately. Self-absorption by SiC grains is a possibility in some cases (Speck et al. 1997a,b), so the fitting procedure was repeated using either a blackbody or modified blackbody, together with silicon carbide in both emission and absorption simultaneously. The results of this fitting are listed in Table 1: 13 of the 20 spectra that could previously be fitted by SiC in pure emission produced better fits with self-absorption included. Four sources found to have SiC absorption features by Speck et al. (1997a) were also re-fitted and the new results are shown at the bottom of Table 1. Two of these four sources required interstellar silicate absorption as well as circumstellar SiC absorption (see Speck et al. 1997a).

The results in Table 1 shows that there is an obvious predominance of the $`\beta `$-SiC phase and that there is now no evidence for the $`\alpha `$-SiC phase at all. This is in contrast to previous attempts to fit the astronomical SiC feature using similar, and in some cases the same, raw laboratory data, but inappropriately corrected for the KBr dispersion. Previous work found that the best fits were obtained with $`\alpha `$-SiC, and had concluded that there was no unequivocal evidence for the presence of any $`\beta `$-SiC. Without the KBr correction, $`\beta `$-SiC matches the observed features, while $`\alpha `$-SiC does not. Thus there is now no astronomical evidence for the presence of $`\alpha `$-SiC in the circumstellar regions around carbon stars. While $`\alpha `$-SiC might exist in small quantities, all observations to date are consistent with the exclusive presence of $`\beta `$-SiC grains. This resolves the past discrepancy, reconciling astronomical observations and meteoritic samples of silicon carbide grains. Having confirmed that SiC grains observed around carbon stars and those found in meteorites are of the same polytype, further discrepancies need to be addressed. In particular, the differences in grain sizes between astronomical models and meteoritic grains merits attention (see Speck et al. 1997a,b for a detailed discussion).

Furthermore, the current work has demonstrated that mineral spectra produced using the DAC thin film method are directly applicable to astrophysical contexts without further manipulation of the data. It is now appropriate to use the DAC thin film method to produce more mineral spectra of use to astronomers.

Support for AKS was provided by the United Kingdom Particle Physics and Astrophysics Research Council and by University College London. Support for AMH was provided by Washington University. We thank Chris Bittner (Superior Graphite Co.) for providing samples, and Tom Bernatowicz for suggesting this collaboration. This paper is dedicated to Dr. Chris Skinner, who died suddenly on October 21st 1997.