# Equilibrial Charge of Grains and Low-temperature Conductivity of Granular Metals.

## Abstract

The low-temperature equilibrial state of a system of small metal grains, embedded into insulator, is studied. We find, that the grains may be charged due to the fluctuations of the surface energy of electron gas in grains, rather than quantization of electron states. The higherst-occupied level in a grain fluctuates within the range of order of charging energy below the overall chemical potential. The system, called a gapless Hubbard insulator, has no overall energy gap, while the transfer of an electron on finite distances costs finite energy. The ionization energy is determined mostly by the intragrain Coulomb repulsion, rather than a weak intergrain interaction, responsible for the Coulomb gap.

The hopping transport in the system is studied. The hopping energy is determined by the charging energy. At low temperature the transport has gapless character.

The hopping conductivity of metal-insulator composite was intensively studied in the past decades. The numerous experiments evidenced typical behavior of conductivity $`\sigma \mathrm{exp}(T_0/T)^{1/2}`$, which needs zero energy gap of the system . It is generally accepted that the energy scale of hopping transport originates from the Coulomb interaction. Two main reasons were put forward, intra- and intergrain e-e repulsion. The first one leads to a Hubbard-like hard gap and constant activation energy of hopping conductivity, the second is responsible for the smooth Coulomb gap. The Coulomb gap requires grains charging at low temperature. At the same time the origin of charging is not clear. In ,  the electrons redistribution was ascribed to the difference of their work functions. This assumption is reasonable relative to the grains of different metals, but this is not the case in the most experiments. Chui  assumed that the fluctuations of level spacing may overweight the charging energy, leading to grains ionization.

Another reason of charging was proposed in. The numerical study of  showed that the large portion of grains should be charged. The charging was attributed to the large variation of the highest-occupied energy level due to the wide fluctuation of level spacing both in integrable and non-integrable systems.

The system of doped semiconductor quantum dots was studied in our work . In this system the dots becomes charged due to fluctuations of local chemical potential, caused by the fluctuations of impurity numbers. This system was evidenced to be a gapless Hubbard insulator.

The purpose of the Letter is the study of low-temperature equilibrial states and hopping transport in a system of large metal grains, embedded in insulator. Unlike to other studies, we want account for the electron quantization in the first order, responsible for the grain surface energy. We argue, that grain charging at low-temperature results from variations of surface energy of electron gas in different grains. We evidenced, that in dependence on the ratio of Coulomb and Fermi energy, the mean charge may exceed the electron charge, producing zero-gap Hubbard insulator. Then we shall study the hopping transport in this system.

Let us discuss the typical parameters of the problem. The charging of a grain with capacitance $`C`$ by an electron costs the energy $`U_c=e^2/2C`$. This energy is less than the energy of e-e interaction on the mean distance between electrons inside grain $`U_0`$, which in most cases is less, than the Fermi energy of bulk metal $`E_F`$. Hence inside grain the electron gas is ideal, while the charging energy $`U_C`$ determines transport properties.

The other important parameter is interlevel distance $`\delta E(\nu V)^1`$, where $`\nu E_F^{1/2}`$ is the density of states of bulk metal, $`V`$ is a grain volume. Since $`CV^{1/3}`$, $`U_c\delta E`$ in a grain, larger than the atomic size. At the same time, the surface energy per electron, found below, is proportional to $`E_FS/VV^{1/3}`$ and remains comparable with $`U_C`$ if $`V\mathrm{}`$. So we shall account for surface energy and neglect the interlevel distance. We shall neglect the collectivization of electron states in different grains also.

Let us consider a metal-insulator composite containing the metal grains with small density $`N`$, $`NV1`$, embedded into insulator with the permittivity $`\kappa `$. Within our model, the grains can exchange by electrons.

The existence of surfaces leads to the surface energy $`\alpha S`$, proportional to the surface $`S`$, additional with respect to the infinite volume. To find the surface tension $`\alpha `$, consider the $`\mathrm{\Omega }`$-potential of free electron gas in a neutral metal grain. Since $`\alpha `$ does not depend on the shape of grain, one can consider a rectangular box. In the limit of large grain size and zero temperature

$`\mathrm{\Omega }={\displaystyle \frac{m^{3/2}(2\mu )^{5/2}}{15\pi ^2\mathrm{}^3}}V+{\displaystyle \frac{m\mu ^2}{8\pi \mathrm{}^2}}S,`$ (1)   
where $`m`$ is electron mass, $`\mu `$ is the local chemical potential. According to (1), the coefficient of surface tension $`\alpha `$ of ideal electron gas is $`\alpha =\frac{m\mu ^2}{8\pi \mathrm{}^2}`$. The ratio of surface energy to the volume energy is determined by the ratio of Fermi wavelength to the system size.

The single-electron spectrum strongly depends on the integrability of the system determined by the grain shape. The $`\mathrm{\Omega }`$-potential (1) does not depend on the shape of grain with fixed volume $`V`$ and surface $`S`$; hence $`\mathrm{\Omega }`$ is not sensitive to the energy spectrum.

For neutrality of a grain the number of electrons $`Z_i=\frac{\mathrm{\Omega }_i}{\mu _i}=\frac{(2m\mu _i)^{3/2}}{3\pi ^2\mathrm{}^3}V_i\frac{m\mu _i}{4\pi \mathrm{}^2}S_i`$ should be equal to the number of ions $`z_i=nV_i`$, where $`n`$ is the density of ions, subscript $`i`$ numbers grains. To be so, the chemical potential should depend on the number of a grain by means of ratio $`S_i/V_i`$. The equalibration of electrochemical potentials $`\mu _ie\varphi _i`$ produces the charges of grains $`e\delta Z_i=e(Z_iz_i)`$, the potentials of grains $`\varphi _i`$ and the shift of the overall chemical potential $`\delta \mu `$ relative to $`E_F`$. The condition of electroneutrality $`\delta Z_i=0`$ yields

$`\varphi _i`$ $`=`$ $`{\displaystyle \frac{e\delta Z_i}{\kappa C_i}},\delta \mu ={\displaystyle \frac{2\alpha }{3n}}{\displaystyle \frac{C_iS_i/V_i}{C_i}},`$ (2)   
$`\delta Z_i`$ $`=`$ $`{\displaystyle \frac{2\alpha \kappa }{3ne^2}}{\displaystyle \frac{C_i}{C_i}}(C_iS_i/V_iC_iS_i/V_i),`$ (3)   
where the anglular brackets denotes the mean value. In the simple case of spherical grains $`C_i=R_i`$.

According to (2,3), the typical charge of grain is determined by the ratio of the Fermi energy to the energy of electron interaction in the metal, multiplied by $`\kappa `$, and if $`R_iRR`$, the charge $`\delta Z_i`$ may be as less, so more than unite.

If $`\alpha \kappa ne^2`$, so the typical $`\delta Z_i1`$, the neglecting of the charge discreetness is not valid and the grains remain neutral. The transition of an electron from grain $`i`$ to grain $`j`$ needs energy $`e^2/2\kappa (1/R_i+1/R_j)`$. As a result, the system of grains proves to be the Hubbard insulator in which the Fermi-excitations are separated by a finite gap from the ground state.

Controversially, if $`\alpha \kappa ne^2`$, the discreetness of charge is unessential in the first approximation. The typical potential of grain has the order of magnitude $`E_F\lambda _F/R`$, and may essentially exceed the temperature. Note, that the level spacing $`\delta E`$ is much less than the typical potential, what proves the used quasiclassical approach.

Really, (3), gives fractional charge. This means that equilibrating of local electrochemical potential takes place with the accuracy of the energy of charging of a grain by a single electron $`U_C`$. The electron redistribution proceeds as long as it is energetically advantageous. The highest occupied energy level $`\mu _i`$ is separated from the overall electrochemical potential $`E_F+\delta \mu `$ by the energy, less than $`U_C`$, while the lowest empty level is above $`\mu _i`$ by $`2U_C`$. Since $`|\delta Z_i|1`$, $`E_F+\delta \mu \mu _i`$ are uniformly distributed within an energy interval $`(0,U_C)`$.

Such state of the system has zero energy gap as a whole, while the transfer of an electron to a finite distance requires finite energy. Thus, the metal-insulator composite may be considered as a gapless Hubbard insulator for $`\alpha \kappa ne^2`$.

Let us consider the conductivity of a composite at low temperature. In the case $`\alpha \kappa ne^2`$ the conductivity is determined by electrons, excited into the upper Hubbard band (and holes in the lower band). Hence the conductivity is purely activating with the activation energy $`min(|\pm U_c\mu |)`$, where $`\mu `$ is in the Hubbard gap.

In the case of gapless Hubbard insulator the general features of transport are similar to the hopping transport in the impurity band.

From the formal point of view, the problem is described by the Miller-Abrahams model in which the atomic levels should be replaced by the highest occupied levels of corresponding grains $`\mu _i`$, and the transition probability is the elastic tunneling probability. The system of equations for external potentials of grains $`\phi _i`$ and currents between grains $`j_{ij}`$ has the usual form $`j_{ij}=eW_{ij}(\phi _i\phi _j)`$, where

$`\mathrm{ln}W_{ij}=\zeta _{ij}=`$   
$`2r_{ij}/a+1/2T(|\mu _i\mu _j|+|\mu _i\mu |+|\mu _j\mu |),`$   
$`r_{ij}`$ is the intergrain distance, $`a`$ is the localization length (the scale of electron wave function decay outside a grain). An electron visits the sites, where the magnitude $`\zeta _{ij}`$ satisfies the connectivity criterion $`\zeta _{ij}<\zeta _c`$.

Due to the continious grain spectrum an electron tunnels from an exited state of one grain to another grain. This process don’t need phonon assistance, as inter-impurity transitions. The process is determined by the density of grains with accessible lowest empty energy levels per unit energy interval $`N/U_C`$, instead of the integral density of states, as hopping transport in the impurity band.

At high enough temperature the tunnel factor will limit the tunneling to the distant grains and the hops to the nearest neighbors will prevail. The characteristic energy is determined by some fracture of $`U_c`$, $`\xi _cU_c`$, where $`\xi _c`$ is the percolation threshold. If assume, that the grains are situated in the square or cubic lattice, $`\xi _c^{(2)}=0.59`$ and $`\xi _c^{(3)}=0.31`$, correspondingly.

At low temperatures electrons prefer to jump to the distant grains, optimizing the activation factor, resulting in the variable range hopping mechanism of transport. The hops goes to the grains for which the logarithms of tunneling probability and activation have the same order. In analogy with 

$$\sigma \mathrm{exp}\left(\frac{T_1}{T}\right)^{1/4},T_1U_cN^1a^3.$$
(4)   
The Formula (4) is valid within the range $`(E_F/Z)^{4/3}T_1^{1/3}TU_c(Na^3)^{1/3}`$. Below the lower limit, the hopping activation energy becomes less than the distance between single-electron levels $`E_F/Z`$ and our assumption about continuous spectrum of states fails. In this limit electrons prefer to jump to the nearest excited levels of the nearest acceptable grains. The typical hopping energy $`\mathrm{\Delta }`$ is determined by the condition that in the volume with radius of the hopping length $`r`$ there is at least one state, belonging to the infinite cluster. The number of accessible states per unite volume in the energy range $`\mathrm{\Delta }`$ is specified by the number of states in one grain $`Z\mathrm{\Delta }/E_F1`$, multiplied by the density of grains, accessible to the electron $`N\mathrm{\Delta }/U_c`$. As a result, we have

$$\sigma \mathrm{exp}\left(\frac{T_2}{T}\right)^{2/5},T_2\left(\frac{E_FU_c}{ZNa^3}\right)^{1/2}.$$
(5)   
The equation (5) obeys the law ”2/5” close to the law ”1/2”, observed in a number of experiments (see, for example, reviews ). Let us emphasize, that unlike the theory of Coulomb gap, caused by a long-range interaction of charges on different grains, our approach takes into account more strong intra-grain charge repulsion. The long-range interaction has the same order of magnitude as considered only near the percolation threshold $`NR^31`$. For Coulomb gap manifestation the temperature should be so low $`T\stackrel{<}{}U_c(NR^3)^{4/9}(Na^3)^{1/3}`$, that the hopping energy to become comparable with interaction of electrons on the neighbor grains. Near the percolation threshold this condition transforms to $`T\stackrel{<}{}U_c(Na^3)^{1/3}`$. In this case the Coulomb gap is essential for transport and leads to the law ”1/2” .

In our consideration we neglected the collectivization of states of different grains assuming the charging energy $`U_c`$ greater than the tunnel amplitude.

We limit ourselves by the effects of the grain shape to the electron redistribution. The other reasons of redistribution are the fluctuations of contents (which were studied earlier in the case of semiconductor quantum dots ), surface states etc.

In conclusion, we evidenced, that in the system of small metal grains they may be charged even in equilibrium at zero temperature. The system may be Hubbard insulator with or without the energy gap depending on whether the surface tension of electron gas is lower or higher than the Coulomb interaction. The conductivity of the gapless insulator at low temperature is determined by the variable range hopping mechanism with the activation energy, caused by the charging energy of grains.

Authors are gratitude to B. Shklovskii for discussions. This work was supported by Russian Foundation for Basic Researches (Grant 97-02-18397).