# Scaling and universality of AC conduction in disordered solids

## Abstract

Recent scaling results for the AC conductivity of ionic glasses by Roling et al. \[Phys. Rev. Lett. 78, 2160 (1997)\] and Sidebottom \[Phys. Rev. Lett. 82, 3653 (1999)\] are discussed. It is shown that Sidebottom’s version of scaling is completely general. A new analytical approximation to the universal AC conductivity of hopping in the extreme disorder limit, the “diffusion cluster approximation,” is presented and compared to simulations and experiments.

Disordered solids have AC electrical properties remarkably in common. These solids, in fact, have so similar frequency-dependent conductivity $`\sigma (\omega )`$ that ionic conduction cannot be distinguished from electronic. Even the temperature-dependence of $`\sigma (\omega )`$ is “quasi-universal.”

The class of disordered solids with quasi-universal AC behavior is large, including polycrystalline and amorphous semiconductors, organic semiconductors, ionic conductive glasses, ionic melts, non-stoichiometric crystals, ionic or electronically conducting polymers, metal cluster compounds, transition metal oxides, and macroscopic mixtures of differently conducting phases like organic-inorganic composites, etc. Each class contains hundreds of different solids and there is a huge literature on their AC conductivities.

It is possible for almost all disordered solids to scale AC data at different temperatures into one single curve. This so-called master curve gives the dimensionless AC conductivity $`\stackrel{~}{\sigma }\sigma (\omega )/\sigma (0)`$ as function of a scaled dimensionless frequency $`\stackrel{~}{\omega }`$. The existence of a master curve is sometimes referred to as the “time-temperature superposition principle” (TTSP). The master curves of different solids - while not identical - are surprisingly similar. This quasi-universality was recognized gradually in the 1970’s .

The common AC features of disordered solids are the following : At low frequencies conductivity is frequency-independent. Around the dielectric loss peak frequency $`\omega _m`$  AC conduction sets in, and for $`\omega \omega _m`$ $`\sigma (\omega )`$ is close to a frequency power-law. The exponent is between 0.7 and 1.0 . As temperature is lowered the exponent goes to 1.0. In a log-log plot the AC conductivity is much less temperature-dependent than the DC conductivity. A final ubiquitous observation is the Barton-Nakajima-Namikawa (BNN) relation  connecting dielectric loss strength $`\mathrm{\Delta }ϵ`$, dielectric loss peak frequency, and DC conductivity - $`\sigma (0)=p\mathrm{\Delta }ϵϵ_0\omega _m`$ \- where $`p`$ is a numerical constant close to one.

To construct the master-curve frequency must be scaled by $`\omega _m`$. Because the dielectric loss strength is only weakly temperature-dependent while $`\sigma (0)`$ and $`\omega _m`$ are both Arrhenius, the BNN-relation implies $`\omega _m\sigma (0)`$. Thus, the existence of a master curve is conveniently summarized into

$$\stackrel{~}{\sigma }=F\left(\frac{C}{\sigma (0)}\omega \right)F(\stackrel{~}{\omega }),$$
(1)   
where $`C`$ may depend on variables like charge carrier concentration $`n`$, temperature $`T`$, high frequency dielectric constant, etc.

Recently, there has been renewed interest in scaling and universality of AC data for ionic glasses  (excellent reviews of glass ionic conduction have been given by Nowick and coworkers  and Ngai ). In 1997 Roling, Happe, Funke, and Ingram showed that $`Cn/T`$ for sodium borate glasses . This year, however, Sidebottom showed that in general scaling is not achieved by $`Cn/T`$ \- instead three quite different ionic conductive systems all obey the following scaling relation ,

$$\stackrel{~}{\sigma }=F\left(\frac{ϵ_0\mathrm{\Delta }ϵ}{\sigma (0)}\omega \right)F(\stackrel{~}{\omega }).$$
(2)   
The purpose of this paper is three-fold. First, we put the recent scaling results into a historical perspective. Second, we show that Eq. (2) is generally valid. Finally, Sidebottom’s experimental master curves are compared to two models, the symmetric hopping model and the macroscopic model. In this connection a new analytical approximation to the universal AC hopping conductivity is presented.

First, the historical perspective. In a series of papers towards the end of the 1950’s Taylor analyzed the dielectric properties of ionic glasses in accordance with the Debye equation with a spread of relaxation times . He showed that the dielectric loss  for all glasses fell on a single plot against scaled frequency. In 1962 Isard relabeled Taylor’s axis by plotting dielectric loss against log of the product of frequency and resistivity and thus essentially arrived at AC scaling in the form given in Eq. (1) . Since then Eq. (1), which we shall refer to as “Taylor-Isard scaling,” has been used in several different contexts. For instance, Taylor-Isard scaling was used by Scher and Lax in 1973 in their famous papers introducing the continuous time random walk approximation , by Summerfield and coworkers in 1985 for amorphous semiconductors , by van Staveren and coworkers in 1991 for metal-cluster compounds , and by Kahnt the same year for ionic glasses .

We now proceed to comment on the scaling principle of Roling and coworkers, $`Cn/T`$ in Eq. (1), and Sidebottom’s recent interpretation of its occasional violations. If $`q`$ is charge, $`f_H`$ jump rate, and $`d`$ jump length, Sidebottom bases his arguments on the expressions $`\sigma (0)nq^2d^2f_H/k_BT`$ and $`\mathrm{\Delta }ϵnq^2d^2/k_BT`$ . Clearly, to obtain $`\stackrel{~}{\omega }`$ frequency should be scaled by $`f_H`$, thus leading to $`Cn/T`$ if all other parameters are constant. But since it is reasonable to assume the jump length would increase as concentration decreases, Sidebottom argues that one cannot expect $`Cn`$; on the other hand the $`n`$-dependence of $`d`$ is taken care of by Eq. (2) in which the unknown jump length is eliminated by scaling with the measured $`\mathrm{\Delta }ϵ`$.

In our opinion Sidebottom’s arguments are largely correct, but Eq. (2) is much more general than it appears from his Letter. Consider hopping of completely non-interacting charge carriers on a cubic lattice. In this model conductivity is $`n`$ times charge carrier mobility and for given lattice jump frequencies the mobility scales with $`d^2`$. This shows that $`Cnd^2`$ as Sidebottom has it. However, if the lattice is homogeneous with just one jump frequency conductivity is frequency-independent; in order to have strongly frequency-dependent conductivity lattice jump frequencies must vary many decades. In such more realistic cases the expressions used by Sidebottom for $`\sigma (0)`$ and $`\mathrm{\Delta }ϵ`$ do not apply - there simply is no unique $`f_H`$. Still, we find in our simulations that these more realistic hopping models always obey Eq. (2). This leads to the question: When is Eq. (2) obeyed?

Equation (2) apparently expresses two informations: 1) TTSP is obeyed, and 2) the scaled frequency is given by $`\stackrel{~}{\omega }=[ϵ_0\mathrm{\Delta }ϵ/\sigma (0)]\omega `$. We now show that 1) mathematically implies 2): TTSP implies the existence of some function $`\stackrel{~}{\sigma }(\stackrel{~}{\omega })`$ where $`\stackrel{~}{\omega }`$ is the scaled frequency. Expanding to first order in $`\stackrel{~}{\omega }`$ leads to $`\stackrel{~}{\sigma }=1+iA\stackrel{~}{\omega }`$ (where $`A`$ is real because $`\sigma ^{}(\omega )=\sigma (\omega )`$). Since $`\sigma =\stackrel{~}{\sigma }\sigma (0)`$ we have $`\sigma =\sigma (0)+iA\stackrel{~}{\omega }\sigma (0)`$. On the other hand, from the definition of $`\mathrm{\Delta }ϵ`$  one has $`\sigma =\sigma (0)+i\omega \mathrm{\Delta }ϵϵ_0`$ for $`\omega 0`$. Equating the two expressions for $`\sigma `$ leads to $`\stackrel{~}{\omega }=A^1[\mathrm{\Delta }ϵϵ_0/\sigma (0)]\omega `$, i.e., Eq. (2)  (the numerical value of $`A`$ is irrelevant). Thus, Eq. (2) follows from TTSP alone.

We next compare the data discussed by Sidebottom to two models, the macroscopic model and the symmetric hopping model. The macroscopic model considers AC conduction in a random mixture of phases with different (frequency-independent) conductivities . The AC conductivity is obtained by solving Maxwell’s equations. Computer simulations have shown  that in the extreme disorder limit (where the local conductivities vary over many decades) the AC conductivity is accurately described by the effective medium approximation (EMA) universality equation ,

$$\stackrel{~}{\sigma }\mathrm{ln}\stackrel{~}{\sigma }=i\stackrel{~}{\omega }.$$
(3)   
The symmetric hopping model , which models AC conduction via random walks of non-interacting particles on a cubic lattice with random symmetric Arrhenius nearest-neighbor jump rates ($`\gamma _0e^{\beta E}`$, where $`E`$ is the random energy barrier), also exhibits universality in the extreme disorder limit. Even for this model does the EMA lead to Eq. (3) . For hopping, however, Eq. (3) does not give an accurate representation of the universal $`\stackrel{~}{\sigma }(\stackrel{~}{\omega })`$ .

Before comparing model predictions to experimental data we present results from new simulations of the symmetric hopping model. The simulations were done on 3-dimensional samples with periodic boundary conditions, using a method based on exactly solving the master equation . Figure 1a shows $`\stackrel{~}{\sigma }^{}`$ \- the real part of $`\stackrel{~}{\sigma }`$ \- for the Box distribution of energy barriers. The frequency axis is scaled according to Eq. (2). Clearly, as $`\beta 1/k_BT`$ increases $`\stackrel{~}{\sigma }^{}`$ converges to a single curve. As seen in Fig. 1b showing the apparent exponent $`\mu `$ ($`\stackrel{~}{\sigma }^{}\stackrel{~}{\omega }^\mu `$) as function of $`\stackrel{~}{\sigma }^{}`$, the universal curve is the same for different energy barrier distributions. Figure 1b compares the simulations to three analytical approximations, the EMA universality equation Eq. (3), the percolation path approximation (PPA) , and a new “diffusion cluster approximation” (DCA), which we describe now:

The reason for AC universality in hopping is the fact that in the extreme disorder limit conduction takes place on the “percolation cluster” formed by the links with largest jump rates until percolation ; the PPA-idea  is to regard the conducting paths on the percolation cluster as strictly one-dimensional. The physical idea behind EMA is to replace the inhomogeneous lattice by an effective homogeneous medium determined self-consistently . Our hopping simulations show that the truth is somewhere between PPA and EMA , somewhere between one-dimensionality and homogeneity. Most likely, this is because both approximations ignore the fact that conduction takes place on some complex subset of the percolation cluster. This “diffusion cluster” must be smaller than the backbone (defined by removing dead-ends of the percolation cluster, fractal dimension=1.7 ) and larger than the set of red bonds (those that, when cut, stops the current, fractal dimension=1.1 ). At present this is all we know about the diffusion cluster and its dimension $`d_0`$ is regarded below as a fitting parameter. To derive the DCA equation we use EMA in $`d_0`$ dimensions. In the extreme disorder limit EMA implies  $`\mathrm{ln}\stackrel{~}{\sigma }s\stackrel{~}{G}`$ where, if $`p(𝐤)=\frac{1}{d_0}_{i=1}^{d_0}\mathrm{cos}(k_i)`$, $`s\stackrel{~}{G}`$ is the following integral $`s\stackrel{~}{G}=_{\pi <k_i<\pi }\frac{d𝐤}{(2\pi )^d}\frac{i\omega }{i\omega +2d_0\sigma [1p(𝐤)]}`$. Whenever $`1<d_0<2`$ one finds $`s\stackrel{~}{G}(i\omega /\sigma )^{d_0/2}`$ at relevant  frequencies. Thus, after rescaling frequency we arrive at the DCA equation,

$$\mathrm{ln}\stackrel{~}{\sigma }=\left(\frac{i\stackrel{~}{\omega }}{\stackrel{~}{\sigma }}\right)^{d_0/2}.$$
(4)   
As is clear from Fig. 1b, the solution of this equation for $`d_0=1.35`$ gives an excellent fit to the universal AC hopping conductivity.

In Fig. 2 the data discussed by Sidebottom  are compared to the macroscopic model represented by the EMA universality equation (3) (dashed line), to the hopping model simulations in the extreme disorder limit (filled squares), and to the DCA (full line, Eq. (4)). Figure 2a shows Sidebottom’s own data for $`(\mathrm{Na}_2\mathrm{O})_\mathrm{x}(\mathrm{GeO}_2)_{1\mathrm{x}}`$ glasses, Fig. 2b shows data for the ionic melt $`0.4\mathrm{Ca}(\mathrm{NO}_3)_20.6\mathrm{KNO}_3`$ measured by Howell and coworkers , and Fig. 2c shows Patel’s data for the thioborate glass system $`(\mathrm{K}_2\mathrm{S})_\mathrm{x}(\mathrm{B}_2\mathrm{S}_3)_{1\mathrm{x}}`$ . In all three systems we find a frequency range where experimental data agree well with the symmetric hopping model.

The symmetric hopping model is an extremely simple model which contains no fitting parameters but still gives a good fit to experimental data as shown above. The model does not include Coulomb interactions and it allows an arbitrary number of charge carriers at each site. We note, however, that the model is mathematically equivalent to that obtained by linearizing (with respect to the electric field) a hopping model with energy disorder and Fermi-statistics . The macroscopic model does not work very well for the ionic systems in Fig. 2. This is interesting because the macroscopic model via Gauss’ law includes all effects of Coulomb interactions. Apparently, the continuum description behind this model does not appropriately reflect the actual microscopic disorder.

To summarize, we have briefly outlined the history of AC scaling in disordered solids and showed that the scaling version Eq. (2) must be obeyed whenever conductivity scaling is possible at all (TTSP obeyed). We have presented a new analytical approximation to the universal AC conductivity of hopping in the extreme disorder limit, the diffusion cluster approximation (DCA), and shown that it gives an excellent fit to simulations . Also, DCA (and thereby the extreme disorder limit of the symmetric hopping model) agrees well with the ionic data discussed by Sidebottom , in a frequency range depending on the system.

###### Acknowledgements.

This work was supported in part by the Danish Natural Science Research Council.