# Spectral Shape of Relaxations in Silica Glass

## Abstract

Precise low-frequency light scattering experiments on silica glass are presented, covering a broad temperature and frequency range ($`9\text{GHz}<\nu <2`$THz). For the first time the spectral shape of relaxations is observed over more than one decade in frequency. The spectra show a power-law low-frequency wing of the relaxational part of the spectrum with an exponent $`\alpha `$ proportional to temperature in the range $`30\text{K}<T<200`$K. A comparison of our results with those from acoustic attenuation experiments performed at different frequencies shows that this power-law behaviour rather well describes relaxations in silica over 9 orders of magnitude in frequency. These findings can be explained by a model of thermally activated transitions in double well potentials.

Relaxations are a characteristic feature of glasses. They show up as a broad quasi-elastic contribution in neutron and light scattering spectra , and also as a damping of sound waves  or as a dielectric loss . Acoustic attenuation, or more precisely the internal friction $`Q^1`$, of silica glass (a-SiO<sub>2</sub>) obtained at different frequencies demonstrates the presence of a broad distribution of relaxation rates . For temperatures above some 10 K it is assumed that relaxations are due to thermally activated transitions in asymmetric double well potentials (ADWP’s) , where the same ADWP’s relax via tunnelling at low temperatures ($`T1`$ K) . Within this model it is possible to extract the distribution of barrier heights $`g(V)`$ from the experimental data .

Although relaxations in silica have been extensively studied so far, a spectroscopic work that covers a broad frequency range is still missing. Acoustic and dielectric studies usually measure at a single frequency only, and spectroscopic techniques like neutron and Raman scattering have typically a low frequency limit around 100 GHz and therefore cover only a small part of the relaxational contribution in a range where it is difficult to extract the spectral shape of relaxations. Recently, it has become possible to obtain low frequency light scattering spectra of glasses at temperatures well below $`T_\mathrm{g}`$, extending the spectral resolution to frequencies below 10 GHz for some polymeric and anorganic glasses .

We refine this approach in order to study the much lower signal levels available for silica. Our data for the first time show the spectral shape of relaxations in silica glass over a broad temperature and frequency range. This enables us to perform a cross test on models about relaxations in glasses, regarding the frequency and temperature dependence of relaxations. Furthermore we will compare our data with internal friction data to examine whether both techniques probe the same kind of relaxations.

Depolarized inelastic light scattering spectra of a sample of Suprasil 300 (synthetic silica, Heraeus, $`<`$1 ppm of OH<sup>-</sup>-groups) were obtained using an Ar<sup>+</sup> laser (514.5 nm, 400 mW) and a six-pass Sandercock tandem Fabry-Perot interferometer . The sample was mounted in a dynamic Helium cryostat. The Suprasil windows of the cryostat are antireflection coated, and the cold windows are mounted tensionless in order to avoid tension induced birefringence. Since the signal levels available from the scattering of silica are much lower than for other glasses studied so far , the optical scheme was improved and optimized for alignment on low intensities . We use a 180 back-scattering geometry with a selection of depolarized scattering. Here the laser beam enters a Glan-Taylor polarizer (extinction 10<sup>-6</sup>) as the extraordinary beam. The polarized component of the light is reflected and focused on the sample. The scattered light is collected by the same lens and passes through the same Glan-Taylor prism, transmitting the depolarized component. The scattered light is collected within an angle of about 4. Special care was taken to avoid contributions to the signal from the windows of the cryostat and the polarizer. This background has been carefully measured for all temperatures and free spectral ranges by recording spectra with and without sample. At all settings we find a background of about 3% of the signal, relating it to a contribution from the cold windows, which are close to the focus of our lens, basically at the same temperature as the sample, and of the same material as the sample. Nevertheless, we carefully eliminated its contribution by subtracting the signal from accumulations without sample from all of our spectra. In a double cross check, for some temperatures we also recorded spectra of a sample of Heralux (fused silica, Heraeus) in a near-to-back-scattering-geometry, avoiding any such contributions. The thus recorded spectra agree with the results reported here within our accuracy.

We recorded spectra with the free spectral ranges (FSR’s) of 1000 GHz and 150 GHz over two spectral ranges on either side of the elastic line. The experimentally determined finesse of the spectrometer is better than 120 and typically about 140. In order to suppress higher transmission orders of the tandem (multiples of 20 FSR’s could give contributions to the signal for a Sandercock tandem FPI ), we use a prism in combination with either of two interference filters of a width of 10 nm and 1150 GHz (FWHM). The contrast of the spectrometer was determined to be better than $`10^9`$ at all frequencies.

To further validate the absence of possible contributions from the instrumental tail of the elastic line or from higher transmission orders of the tandem, we measured spectra for both FSR’s at a low temperature, $`T=6`$ K. At this temperature the anti-Stokes part of the spectrum should be almost zero because either the Bose factor or the signal itself are very low for this temperature. Indeed, the anti-Stokes part of the spectrum at this temperature shows no deviations from the dark count level of 2.47 counts/s of our detector, demonstrating the absence of contributions of higher orders or from the elastic line. Any contributions from higher orders are especially problematic for the smaller FSR, because the signal is much higher at frequencies of multiples of 20 of this FSR than in the range of interest: the signal increases with increasing frequency, especially at low temperatures, where the relaxational contribution is small (cf. Fig. 1). For our 6 K-spectrum in this region the sum of the signal and possible higher order contributions is less than 0.3 counts/s, ie, it is absent within the precision of our experiment. Since the vibrational part, that could lead to any parasitic contributions, rises much slower with temperature than the signal from relaxations, it is clear that signals from higher transmission orders do not disturb our spectra.

The upper part of Figure 1 displays the intensity of the depolarized back-scattering spectra of silica. At high frequencies the Boson peak is observed. The signal passes through a minimum and shows features of a central peak. At frequencies of 35 GHz and 20 GHz two narrow peaks are observed that correspond to the longitudinal and transversal Brillouin lines and are due to a leakage from imperfect polarisation and to the finite aperture, respectively. Apart from the Brillouin lines, the central peak shows a power-law frequency dependence, and its shape considerably changes with temperature.

In the susceptibility representation, $`\chi ^{\prime \prime }(\nu )=I/(n(\nu )+1)`$ of the Stokes side, the trivial temperature dependence due to the Bose factor $`n(\nu )`$ is eliminated. The susceptibility data in Figure 1 have been smoothed by adjacent averaging over five points. The presence of two contributions to the low-frequency light scattering in glasses can be distinguished by the different temperature dependence: the vibrational contribution dominates at high frequencies and scales with the Bose factor (ie, the susceptibility is temperature independent), wheras the relaxational spectrum that dominates at lower frequencies strongly changes with temperature. As can be seen by the crossing of the spectra at different temperatures, this is not simply due to an increase of the susceptibility with temperature as would be expected in the case of higher-order scattering processes. For all temperatures, the low-frequency wing of our spectra shows a power-law behaviour. The temperature dependence of the exponent, $`\alpha (T)`$, is shown in the inset of Figure 2: $`\alpha `$ is proportional to temperature up to 200 K, with $`\alpha =T/319`$ K.

Let us see if this frequency and temperature dependence of relaxations can be described within our present understanding of glasses. In 1955 Anderson and Bömmel attributed relaxations in silica to thermally activated processes with a broad distribution of relaxation times . Theodorakopoulos and Jäckle calculated the light scattering due to structurally relaxing two-state defects and show its relation to the acoustic attenuation . This approach was refined by Gilroy and Phillips , who consider thermally activated transitions in ADWP’s. The potential wells are assumed to be the same that at lower temperatures ($`T1`$ K) relax via tunnelling and are responsible for the low temperature anomalies of glasses, ie, the parameters for the potential wells are taken from the tunnelling model . Following the assumption that the distribution of asymmetry parameters $`\mathrm{\Delta }`$ is flat, the light scattering susceptibility $`\chi ^{\prime \prime }(\nu )`$ and the internal friction $`Q^1`$ only depend on the distribution of barrier heights $`g(V)`$ :

$$\chi ^{\prime \prime }(\nu )Q^1\underset{0}{\overset{\mathrm{}}{}}\frac{2\pi \nu \tau }{1+(2\pi \nu \tau )^2}g(V)𝑑V.$$
(1)   
Here the relaxation time $`\tau =\tau _0\mathrm{exp}(V/k_\mathrm{B}T)`$,where $`\tau _0`$ is the fastest relaxation time that occurs. Assuming an exponential distribution of barrier heights, $`g(V)=V_0^1\mathrm{exp}(V/V_0)`$, the model predicts for the low frequency wing of the relaxation spectrum, $`\nu (2\pi \tau _0)^1`$, a power-law susceptibility spectrum with an exponent proportional to temperature : $`\alpha =k_\mathrm{B}T/V_0`$. The inset of Figure 2 shows that the exponents of our silica data agree with the model for temperatures below 200 K and we obtain $`V_0/k_\mathrm{B}=319`$ K. At 300 K the observed exponent is less than expected from the model. Since the exponent of the susceptibility cannot become higher than 1 for

relaxation processes and is already close to 1 at room temperature, the deviation at 300 K comes as no surprise. Indeed at higher temperatures up to $`T_\mathrm{g}`$ it is found that the exponent remains constant at 1 . The simple assumption of thermally activated relaxations over barriers with an exponential distribution of barrier heights can therefore well account for the observed temperature dependence of the spectral shape of the low-frequency light scattering data of silica at temperatures up to 200 K.

Within the model of Theodorakopoulos and Jäckle the distribution of activation energies is reflected in the light scattering susceptibility just in the same manner as in the internal friction (ie, $`\chi ^{\prime \prime }(\nu )Q^1`$, cf. Eq. 1) . Taking the internal friction at a frequency that is also accessible to light scattering spectroscopy, the proportionality constant can be eliminated in order to directly compare the results of both techniques. In Figure 2 we plot the susceptibility data of Figure 1 scaled to the internal friction measured at 35 GHz ; a single factor can be used for all spectra, showing that the temperature dependence of $`\chi ^{\prime \prime }(\nu )`$ around 35 GHz is the same as that of the internal friction. Acoustic data from different experiments have a scatter of about a factor of two, and within a factor of two follow the extrapolations of the light scattering data. It appears that relaxations indeed show up in the same manner for both techniques, and that with good approximation the spectral shape of relaxations in silica shows a power-law behaviour with an exponent $`\alpha =T/319`$K over the whole available frequency range $`500\text{Hz}<\nu <500`$ GHz.

This can be further demonstrated by comparing the distributions $`g(V)`$ of the barrier heights obtained from the different experiments. Equation 1 can be further simplified, assuming a broad distribution of barrier heights $`g(V)`$. In this case the

susceptibility spectrum $`\chi ^{\prime \prime }(\nu )`$ and the internal friction $`Q^1(T)`$ for $`2\pi \nu \tau _01`$ directly reflect the distribution of correlation times, and thus the distribution $`g(V)`$ :

$$\chi ^{\prime \prime }Q^1Tg(V),\text{where}V=k_\mathrm{B}T\mathrm{ln}(1/2\pi \nu \tau _0).$$
(2)   
Assuming that $`g(V)`$ is temperature independent and that thermally activated transitions determine the light scattering spectra and the internal friction at temperatures above some 10 K, this distribution of barrier heights can be directly extracted from the data by rescaling the axes with $`T`$. Explicitly, we multiply the $`\mathrm{log}(\nu )`$-axis by $`T`$ and divide the $`Q^1`$ and $`\chi ^{\prime \prime }`$ axes by $`T`$.

Then a master curve for $`g(V)`$ should result for the rescaled $`\chi ^{\prime \prime }(\nu )`$ spectra and of the acoustic data $`Q^1(T)`$ for the different frequencies. Since the amplitude of the light scattering data has already been fixed with respect to the acoustic data, the only parameter for the rescaling is $`\nu _0=(2\pi \tau _0)^1`$. Unlike the acoustic experiments our spectra cover this cut-off frequency at the transition from the power-law relaxational contribution to the vibrations in the range of the boson peak (cf. Fig. 1). From the light scattering spectra we obtain $`\nu _0=800`$ GHz (ie, $`\tau _0=0.2`$ ps), which is in good agreement with previous results taken from acoustic data , and use this value for the rescaling of all the data. For the rescaling of the light scattering data we use the frequency range where the power-law holds and where the contribution from vibrations to the spectra is negligible. In principle, the distribution $`g(V)`$ can be obtained from a single experiment at one frequency (cf. eg, ). The light scattering experiment, however, probes the temperature and frequency dependence of the susceptibility simultaneously, allowing a cross test of the model .

Figure 3 shows the result of this rescaling procedure. The light scattering data form the different temperatures show an excellent agreement and the exponential distribution as discussed above. Within the scatter of the acoustic data of about a factor of two, we obtain a master curve for all the available data ($`10\text{K}<T<200`$ K). The rescaling of the abscissa involves both the temperature and the frequency of the data. Therefore at a fixed barrier height of say $`V/k_\mathrm{B}=200`$ K, we compare data that have been obtained at a temperature of 200 K and a frequency of about 200 GHz with those obtained at a temperature of 10 K and a frequency of 500 Hz. Considering this range, it is indeed surprising that the scaling works so well. The rescaled acoustic data cover the range both above and below the temperature of the loss peak found in silica at temperatures between some 25 and 130 K . (In Fig. 2 the precence of this peak is not seen at low frequencies, because the lowest temperature plotted is 32 K.) Taking acoustic data alone, it was found that a modified Gaussian distribution describes the data better than the exponential distribution obtained from our light scattering data . This is demonstrated by the fact that some of the acoustic data show a slight curvature on the semi-logarithmic plot in Figure 3, which is absent for the rescaled light scattering data . However, the simple model with only two parameters, $`\tau _0`$ and $`V_0`$, rather well describes relaxations in silica over a broad temperature and frequency range.

In conclusion, we extend existing light scattering data on silica by about one order of magnitude to lower frequencies, covering a broad range in temperature down to some 20 K. Our data for the first time reveal the spectral shape of relaxations over more than one decade in frequency, where relaxations clearly dominate over the vibrational contribution to the spectrum. The relaxations show a power-law spectral shape at low frequencies with an exponent $`\alpha `$ proportional to temperature. For the temperature range below 200 K our data are in good quantitative agreement with a model attributing relaxations in glasses to thermally activated transitions with an exponential distribution of barrier heights $`g(V)`$. We further compare the light scattering susceptibility $`\chi ^{\prime \prime }(\nu )`$ with the internal friction $`Q^1`$ and find that within a factor of two the power-law behaviour extends down to frequencies of some 500 Hz. Therefore relaxations in silica within the temperature range $`10\text{K}T200\text{K}`$ can be described by two single parameters, $`\nu _0=800`$ GHz and $`V_0/k_\mathrm{B}=319`$ K, for all frequencies extending up to the onset of the boson peak. Although it is known that this model in its simplest form presented here does not work for all glasses , we believe that our demonstration that the model works remarkably well for silica, a paradigmatic glass, should be considered in any refinement of models describing relaxations in glasses.

We thank V. N. Novikov and N. V. Surovtsev for many illuminating discussions and the DFG (SFB 279) for financial support. J. W. appreciates financial support from H. Wiedersich.