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# Generalized Drude model: Unification of ballistic and diffusive electron transport

## I Introduction

Electron transport in semiconducting structures is ballistic if the mean free path is much larger than the characteristic dimensions of the sample, and it is diffusive if the mean free path is much smaller than these. In the first case, there is no impurity or lattice scattering, and the current is determined by the ballistic motion in the electric field ; in the second case, scattering predominates and is described within the drift-diffusion scheme . In many cases of physical relevance, however, the mean free path is neither large nor small compared with the characteristic dimensions of the sample. Thus, formulas for the current-voltage characteristic have appeared in the literature which combine features of the two limiting types of transport mechanism for particular conduction band edge profiles, e.g., for a single barrier .

In the present paper, we consider electron transport in parallel-plane semiconducting structures, i.e., structures whose parameters vary in one direction only. We develop a one-dimensional transport model which is valid for any magnitude of the mean free path and any form of the band edge profile, and thus unifies the ballistic and diffusive transport mechanisms. It is based on the idea that the electrons move ballistically in the electric field over intervals with average length equal to a universal mean free path, after which they are thermalized into a state of local equilibrium characterized by a quasi-Fermi level (electrochemical potential). The length of the sample is made up of random configurations of such ballistic intervals. Averaging over these configurations results in a unified description of electron transport, in which purely ballistic and purely diffusive transport appear as limiting cases. We work within the semiclassical approach , which allows a concise and transparent formulation. However, quantum tunneling (“thermionic field emission” ) is taken into account in WKB approximation.

The description of transport in terms of ballistic motion over intervals of the average length of the mean free path with thermalization at the end is, of course, also the basis of the Drude model  and of the relaxation-time approximation of the Boltzmann equation. There, however, the further development makes use of the assumption that the mean free path is small compared to the characteristic dimensions of the sample, leading to a diffusive description of the transport. In contrast to this, such an assumption is not made in the present work, and the magnitude of the mean free path relative to the sample dimensions determines the relative importance of the ballistic and diffusive transport mechanisms. The unified description thus is a generalization of the Drude model; it is particularly relevant to polycrystalline and microcrystalline materials (in the following indiscriminately referred to as “polycrystalline materials”) when the grain size is comparable to, or smaller than, the mean free path. In this case, the grains must not be considered separately and the sample must be treated as a whole.

Our approach is the semi-phenomenological one commonly used in the description of transport in semiconductor devices (cf., e.g., Ref. ). Its prominent and useful feature is that its results are obtained in closed form, which allows one to analyze the physics of the transport process in a transparent way. We have been able to formulate our model in one dimension. For transport across parallel-plane structures as considered in the present work, a fully three-dimensional treatment of the thermalization process is expected not to change the resulting formulas in a substantial way (cf. Sec. III.D below for a more detailed discussion of this point).

In the following section, we introduce the basic assumptions of the unified model and explain the procedure of averaging over the random configurations of ballistic intervals across which the electrons travel without scattering. In Sec. III, we present our principal result: a universal formula for the current-voltage characteristic reflecting the interplay of ballistic and diffusive transport. This formula generalizes previous expressions proposed for a single barrier. Its distinctive new feature is the appearance of a shape term that depends on the detailed structure of the band edge profile and also explicitly on the mean free path. This term is essential, e.g., for the description of transport in polycrystalline materials. Section IV deals with two numerical examples. First, we investigate chains of identical grains in polycrystalline materials. Here, the effect of the relative magnitudes of mean free path and characteristic length of the sample, i.e., the relative importance of the ballistic and diffusive mechanisms, is demonstrated explicitly. It is found that the (zero-bias) conductivity, defined as conductance times sample length, generally depends upon the number of grains in the sample. Second, as an example of a degenerate system, we discuss the grain barrier conductance of a highly doped polycrystalline material as a function of temperature. Section V contains a summary and some concluding remarks.

## II The model

### A Basic formulation

The unified model is based on the following one-dimensional scheme (cf. Fig. 1). The length of the sample (extending from $`x=0`$ to $`x=S`$) is covered by a chain of $`N`$ intervals $`\{i\}`$ with end points $`x_{i1}^N`$ and $`x_i^N`$, $`i=1,\mathrm{},N`$ ($`x_i^N>x_{i1}^N;x_0^N=0,x_N^N=S`$) across which the electrons move ballistically in the field of the conduction band edge potential $`E_\mathrm{c}(x)`$. There may be any number of intervals in a chain, $`N=1,\mathrm{},\mathrm{}.`$ At the end points of these “ballistic intervals” (in particular, at the fixed end points of the sample), the electrons are equilibrated (thermalized). These points of local equilibrium are theoretical constructs which may be thought to be connected via thin ideal leads (flat potentials) to large ideal reservoirs in equilibrium, with chemical potentials equal to the quasi-Fermi level at the points . The current flow in a ballistic interval is assumed to result from the injection of electrons at the end points and their transmission through the interval, in line with Landauer’s view of conduction as a transmission phenomenon .

The current in the ballistic interval $`\{i\}`$ is given by

$$j(i)=e_0^{\mathrm{}}𝑑ϵ\left[T_i^\mathrm{L}(ϵ+E_\mathrm{c}(x_{i1}))f(x_{i1}^N;ϵ)T_i^\mathrm{R}(ϵ+E_\mathrm{c}(x_i))f(x_i^N;ϵ)\right],i=1,\mathrm{},N,$$
(1)
where $`f(x;ϵ)`$ is the phase space density of the electrons at position $`x`$ with kinetic energy $`ϵ`$ of the motion in the $`x`$-direction, and $`T_i^\mathrm{L}(E)`$ is the (classical or quantal) probability for ballistic transmission at total energy $`E`$ from $`x_{i1}^N`$ to $`x_i^N`$ \[reversely for $`T_i^\mathrm{R}(E)`$\]. Owing to time reversal invariance we have $`T_i^\mathrm{L}(E)=T_i^\mathrm{R}(E)[=T_i(E)]`$. For Boltzmann statistics (nondegenerate regime), we have $`f(x;ϵ)=(4\pi m^{}/\beta h^3)\mathrm{exp}\{\beta [ϵ+E_\mathrm{c}(x)E_\mathrm{F}(x)]\}`$, and obtain from Eq. (1)

$$j(i)=ev_\mathrm{e}N_\mathrm{c}𝒯(i)\left[e^{\beta E_\mathrm{F}(x_{i1}^N)}e^{\beta E_\mathrm{F}(x_i^N)}\right],i=1,\mathrm{},N;$$
(2)
here, $`v_\mathrm{e}=(2\pi m^{}\beta )^{1/2}`$ is the emission velocity, the factor $`N_\mathrm{c}=2(2\pi m^{}/\beta h^2)^{3/2}`$ is the effective density of states at the conduction band edge, $`E_\mathrm{F}(x)`$ is the quasi-Fermi level at position $`x`$, and $`\beta =1/k_\mathrm{B}T`$. The factor $`𝒯(i)`$ is the thermally averaged probability for ballistic transmission across the interval $`\{i\}`$,

$$𝒯(i)=\beta _{E_\mathrm{c}^{(i)}}^{\mathrm{}}𝑑Ee^{\beta E}T_i(E),$$
(3)
where $`E_\mathrm{c}^{(i)}=\mathrm{max}\{E_\mathrm{c}(x_{i1}),E_\mathrm{c}(x_i)\}`$ (cf. Ref. , and Ref. , Sec. 2.1).

In the classical description, we have $`T_i(E)=\mathrm{\Theta }(EE_\mathrm{c}^\mathrm{m}(i))`$, where $`E_\mathrm{c}^\mathrm{m}(i)`$ is the maximum of the conduction band edge profile $`E_\mathrm{c}(x)`$ between or at the points $`x_{i1}^N`$ and $`x_i^N`$. Therefore, Eq. (2) becomes

$$j(i)=ev_\mathrm{e}N_\mathrm{c}e^{\beta E_\mathrm{c}^\mathrm{m}(i)}\left[e^{\beta E_\mathrm{F}(x_{i1}^N)}e^{\beta E_\mathrm{F}(x_i^N)}\right],i=1,\mathrm{},N.$$
(4)
In what follows, we adhere to the classical description since it allows the greatest transparency, in particular as far as the averaging over ballistic intervals is concerned. The full formulation including tunneling effects will be presented in Sec. III.B.

In the stationary case, the current is independent of position, $`j(i)=j=`$ const., and we can write Eq. (4) in the form

$$e^{\beta E_\mathrm{F}(x_i^N)}=e^{\beta E_\mathrm{F}(x_{i1}^N)}+\frac{j}{ev_\mathrm{e}N_\mathrm{c}}e^{\beta E_\mathrm{c}^\mathrm{m}(i)},i=1,\mathrm{},N.$$
(5)
Iterating this relation, we find for a configuration with $`N`$ ballistic intervals

$$e^{\beta E_\mathrm{F}(S)}e^{\beta E_\mathrm{F}(0)}=\frac{j}{ev_\mathrm{e}N_\mathrm{c}}\underset{i=1}{\overset{N}{}}e^{\beta E_\mathrm{c}^\mathrm{m}(i)}.$$
(6)
The sum on the right-hand side must be averaged over all possible configurations of the ballistic intervals, i.e., over all positions of their end points $`x_i^N`$ $`(i=1,\mathrm{},N1)`$ in the chain of $`N`$ intervals, where $`N=1,\mathrm{},\mathrm{}`$. Introducing the absolute maximum $`E_\mathrm{c}^\mathrm{m}`$ of the band edge profile $`E_\mathrm{c}(x)`$ in the interval $`[0,S]`$, we denote the product of $`\mathrm{exp}(\beta E_\mathrm{c}^\mathrm{m})`$ with the average of the sum by $`\mathrm{\Xi }`$,

$$\mathrm{\Xi }=\underset{i=1}{\overset{N}{}}e^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}^\mathrm{m}(i)]}_{\{N,x_i^N\}}.$$
(7)
Setting $`E_\mathrm{F}(0)E_\mathrm{F}(S)=eV`$, we then have

$$1e^{\beta eV}=\frac{j}{ev_\mathrm{e}N_\mathrm{c}}e^{\beta E_\mathrm{p}}\mathrm{\Xi },$$
(8)
where $`E_\mathrm{p}=E_\mathrm{c}^\mathrm{m}E_\mathrm{F}(0)`$ is the overall barrier height. The end points of the sample are connected to large ideal reservoirs in equilibrium characterized by the Fermi levels $`E_\mathrm{F}(0)`$ and $`E_\mathrm{F}(S)`$ whose difference determines the voltage bias $`V`$ .

### B Averaging over the ballistic configurations

#### 1 The distribution of the ballistic intervals

The distribution of a set of $`N`$ ballistic intervals, i.e., of the points of equilibrium $`x_i^N`$, across the sample of length $`S`$ is determined in the following way. The probability of an electron to make a collision in the interval $`d\xi `$ after having traversed a distance $`\xi `$ since its last collision is given by $`\mathrm{exp}(\xi /l)(d\xi /l)`$, where $`l`$ is the mean free path . Assuming (as in the Drude model) that an electron which collides with an impurity is taken out of the ballistic current and can be counted as equilibrized, we write the complete distribution of the ballistic intervals in the form of an infinite-dimensional diagonal matrix with elements labelled by the number $`N`$ of ballistic intervals, $`N=1,2,\mathrm{}`$ :

$$d𝐏=\{e^{S/l},\mathrm{},\left[\underset{i=1}{\overset{N1}{}}\frac{dx_i^N}{l}e^{(x_i^Nx_{i1}^N)/l}\theta (x_i^Nx_{i1}^N)\right]e^{(Sx_{N1}^N)/l},\mathrm{}\}=\{\mathrm{},dP_N,\mathrm{}\};$$
(9)
here the exponents in the general term cancel out except for the term $`(S/l)`$, and we have (recalling $`x_0^N=0`$)

$$dP_1=e^{S/l};dP_N=e^{S/l}\underset{i=1}{\overset{N1}{}}\frac{dx_i^N}{l}\theta (x_i^Nx_{i1}^N)\mathrm{for}N2.$$
(10)
This distribution is normalized to unity, since

$$\mathrm{Tr}𝑑𝐏=\left(1+\underset{N=2}{\overset{\mathrm{}}{}}_0^S\frac{dx_1^N}{l}_{x_1^N}^S\frac{dx_2^N}{l}\mathrm{}_{x_{N2}^N}^S\frac{dx_{N1}^N}{l}\right)e^{S/l}=1.$$
(11)
Here, the infinite sum over $`N`$ contains power terms which add up to the exponential exp$`(S/l)`$; the evaluation of all quantities considered in the following runs along similar lines.

The average sum (7) can be written as an expectation value of the form

$$\mathrm{\Xi }=\underset{i=1}{\overset{N}{}}e^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}^\mathrm{m}(i)]}_{\{N,x_i^N\}}=\mathrm{Tr}𝑑𝐏𝚺,$$
(12)
where we have introduced the infinite-dimensional diagonal matrix

$$𝚺=\{\mathrm{},\underset{i=1}{\overset{N}{}}e^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}^\mathrm{m}(i)]},\mathrm{}\},N=1,2,\mathrm{}.$$
(13)
#### 2 The average for a peak in $`E_\mathrm{c}(x)`$

The case where the conduction band edge profile $`E_\mathrm{c}(x)`$ has a single peak at the position $`X`$ somewhere along the sample is illustrated in Fig. 1. If a ballistic interval $`\{i\}`$ contains $`X`$, we have $`E_\mathrm{c}^\mathrm{m}(i)=E_\mathrm{c}(X)`$; if it lies to the left \[right\] of $`X`$, we have $`E_\mathrm{c}^\mathrm{m}(i)=E_\mathrm{c}(x_i^N)`$ $`[=E_\mathrm{c}(x_{i1}^N)]`$. Thus we obtain for the average sum

$`\mathrm{\Xi }`$ $`=`$ $`{\displaystyle \underset{N=1}{\overset{\mathrm{}}{}}}{\displaystyle 𝑑P_N\underset{i=1}{\overset{N}{}}e^{\beta E_\mathrm{c}^\mathrm{m}}\left[e^{\beta E_\mathrm{c}(x_i^N)}\theta (Xx_i^N)+e^{\beta E_\mathrm{c}(X)}\theta (x_i^NX)\theta (Xx_{i1}^N)+e^{\beta E_\mathrm{c}(x_{i1}^N)}\theta (x_{i1}^NX)\right]}`$ (14)
$`=`$ $`1+\stackrel{~}{S}/l,`$ (15)
where $`E_\mathrm{c}^\mathrm{m}=E_\mathrm{c}(X)`$ in the “reduced sample length”

$$\stackrel{~}{S}=_0^S𝑑xe^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}(x)]}$$
(16)
satisfying $`\stackrel{~}{S}S`$. Special cases are $`X=0`$ and $`X=S`$, when the profile is monotonic.

It is seen that the average sum $`\mathrm{\Xi }`$ for a profile containing a single maximum at a position $`X`$ inside or at the end of the sample, is given by unity plus the ratio of reduced sample length and mean free path. By the definition of the average sum $`\mathrm{\Xi }`$, the unit term represents the contribution of the ballistic transmission across the highest peak $`E_\mathrm{c}^\mathrm{m}`$ of the profile $`E_\mathrm{c}(x)`$.

#### 3 The average for a valley in $`E_\mathrm{c}(x)`$

We consider a conduction band edge profile of the type shown in Fig. 2. It contains two peaks at $`X_0`$ and $`X_1`$, respectively (without loss of generality, the left peak is assumed to be the higher one), and in between a valley with minimum at $`Y_1`$. The average sum over the ballistic intervals enclosed by the peaks $`(X_0x_{i1}^N`$; $`x_i^NX_1)`$ is given by

$`\mathrm{\Xi }`$ $`=`$ $`{\displaystyle \underset{N=1}{\overset{\mathrm{}}{}}}{\displaystyle }dP_N{\displaystyle \underset{i=1}{\overset{N}{}}}e^{\beta E_\mathrm{c}^\mathrm{m}}\{e^{\beta E_\mathrm{c}(x_{i1}^N)}\theta (Y_1x_i^N)+e^{\beta E_\mathrm{c}(x_i^N)}\theta (x_{i1}^NY_1)`$ (17)
$`+[e^{\beta E_\mathrm{c}(x_{i1}^N)}\theta (x_{i1}^Nx_i^N)+e^{\beta E_\mathrm{c}(x_i^N)}\theta (x_{i1}^Nx_i^N)]\theta (x_i^NY_1)\theta (Y_1x_{i1}^N)\},`$ (18)
where $`x^{}`$ is that position to the right (left) of $`Y_1`$ where the profile has the same height as at the point $`x`$ to the left (right) of $`Y_1`$. The average sum over the ballistic intervals contributed by the left-hand peak at $`X_0`$ is given by Eq. (15) with $`X=X_0`$ and the last term in the brackets omitted, and analogously for the right-hand peak at $`X_1`$. The average sum for the profile of Fig. 2 can then be evaluated as

$$\mathrm{\Xi }=1+\stackrel{~}{S}/l+_{X_1^{}}^{X_1}\frac{dx}{l}e^{|xx^{}|/l}e^{\beta E_\mathrm{c}(X_0)}\left[e^{\beta E_\mathrm{c}(X_1)}e^{\beta E_\mathrm{c}(x)}\right],$$
(19)
where now $`E_\mathrm{c}^\mathrm{m}=E_\mathrm{c}(X_0)`$ in $`\stackrel{~}{S}`$.

It is seen from this formula that for $`b_{0,1}lw_1`$, where $`w_1=X_1X_1^{}`$ is the width of the valley and $`b_{0,1}`$ are the “widths” of the two barriers at $`X_{0,1}`$, the integral over the second exponential in the brackets can be neglected. Since

$$_{X_1^{}}^{X_1}𝑑xe^{|xx^{}|/l}=l(1e^{w_1/l})l,$$
(20)
we obtain

$$\mathrm{\Xi }=1+\stackrel{~}{S}/l+e^{\beta [E_\mathrm{c}(X_0)E_\mathrm{c}(X_1)]},$$
(21)
i.e., we have independent contributions from each peak (first and third terms).

On the other hand, for $`Sl`$ (ballistic regime), the whole integral term in Eq. (19) can be neglected (together with the term $`\stackrel{~}{S}/l`$) since it is smaller than $`(w_1/l)\mathrm{exp}\{\beta [E_\mathrm{c}(X_0)E_\mathrm{c}(X_1)]\}`$. Then $`\mathrm{\Xi }`$ reduces to the unit term, which represents the contribution of the transmission across the higher peak at $`X_0`$: this peak “eclipses” the lower peak at $`X_1`$.

## III Current-voltage characteristic

### A Classical current-voltage characteristic

In the foregoing, we have considered single peaks and valleys. If the profile contains not just one, but an arbitrary combination of such structures as in a chain of grains in polycrystalline materials, the average sum $`\mathrm{\Xi }`$ for a general band edge profile is given by

$$\mathrm{\Xi }=1+(\stackrel{~}{S}+\stackrel{~}{\mathrm{\Lambda }})/l,$$
(22)
where we have introduced the “shape term” $`\stackrel{~}{\mathrm{\Lambda }}`$ for $`M`$ valleys,

$$\stackrel{~}{\mathrm{\Lambda }}=\underset{v=1}{\overset{M}{}}_{X_v^{}}^{X_v}𝑑xe^{|xx^{}|/l}e^{\beta E_\mathrm{c}^\mathrm{m}}\left[e^{\beta E_\mathrm{c}(X_v)}e^{\beta E_\mathrm{c}(x)}\right].$$
(23)
The contribution of valley $`v`$ (with adjoining lower maximum $`X_v`$) consists of an integral which extends over the width of the valley from $`X_v^{}`$ to $`X_v`$. We now define the effective transport length $`L=\mathrm{\Xi }l`$, so that

$$L=l+\stackrel{~}{S}+\stackrel{~}{\mathrm{\Lambda }}.$$
(24)
In compliance with Eq. (20), we find $`\stackrel{~}{\mathrm{\Lambda }}<S`$.

From Eqs. (8), (22) and (24), we obtain the classical current-voltage characteristic for nondegenerate systems as

$$j=ev_\mathrm{e}N_\mathrm{c}e^{\beta E_\mathrm{p}}\frac{l}{L}(1e^{\beta eV}).$$
(25)
This formula is the principal result of the present work. It is given here in the context of classical transport, where its interpretation is most perspicuous; corrections due to tunneling will be introduced below.

The properties of the current-voltage characteristic (25) are determined by the barrier height $`E_\mathrm{p}`$ and the ratio $`l/L`$. In Eq. (24) for the effective transport length $`L`$, the mean free path $`l`$ represents the ballistic contribution to the current (this term is associated with the highest peak of the band edge profile). The remaining terms give a quantitative measure of the influence of that part of the electron motion which is not purely ballistic. Their contribution amounts to at most twice the length $`S`$ of the sample. The reduced sample length $`\stackrel{~}{S}`$ given by Eq. (16) represents a contribution that characterizes the band edge profile $`E_\mathrm{c}(x)`$ in an integral way; it does not manifestly depend on $`l`$, only indirectly so via the profile (cf. below). The shape term $`\stackrel{~}{\mathrm{\Lambda }}`$ given by Eq. (23), on the other hand, depends on the detailed structure of the profile as well as explicitly on the mean free path and thus represents the interplay of ballistic and diffusive transport. This term is a distinctive feature of formula (25).

We emphasize that the integrals appearing in the effective transport length $`L`$, and in particular the reduced sample length $`\stackrel{~}{S}`$, result from averaging over ballistic configurations, not because $`l`$ were so small that the sum over intervals could be replaced with an integral, as assumed in the diffusive regime.

The barrier height $`E_\mathrm{p}`$ and the effective transport length $`L`$ are determined by the band edge profile $`E_\mathrm{c}(x)`$ which is a solution of the Poisson equation

$$E_\mathrm{c}^{\prime \prime }(x)=\frac{e}{ϵ_\mathrm{s}}[en(x)+Q(x)],$$
(26)
where

$$n(x)=N_\mathrm{c}e^{\beta [E_\mathrm{c}(x)E_\mathrm{F}(x)]}$$
(27)
is the conduction electron density and $`Q(x)`$ is the density of fixed charges. In the “trapping model” for grain boundaries in polycrystalline materials , which our calculations in Sec. IV are based upon, the density $`Q(x)`$ is given by

$$Q(x)=eN_{\mathrm{don}}+\underset{v=1}{\overset{M}{}}q_v^\mathrm{t}\delta (xX_v),$$
(28)
where $`N_{\mathrm{don}}`$ is the density of donor atoms (assumed completely ionized), and $`q_v^\mathrm{t}`$ is the area density of the charge associated with occupied acceptor-like “trapping states” localized at the grain boundary at $`X_v`$. The donor density $`N_{\mathrm{don}}`$ not only affects the band edge profile $`E_\mathrm{c}(x)`$, but also determines the magnitude of the mean free path $`l`$ (a simple relation between $`l`$ and $`N_{\mathrm{don}}`$ is obtained from the analytical expression for the $`N_{\mathrm{don}}`$-dependence of the electron mobility $`\mu `$ given in Ref. , using $`\mu =ev_\mathrm{e}\beta l`$). Thus, there is, in general, an indirect relation between $`E_\mathrm{c}(x)`$ and $`l`$, which implies an indirect (and generally rather strong) $`l`$-dependence of the barrier height $`E_\mathrm{p}`$ as well as of the reduced sample length $`\stackrel{~}{S}`$ and the shape term $`\stackrel{~}{\mathrm{\Lambda }}`$ \[as noted above, the latter term also depends explicitly on $`l`$, namely via the weight function $`\mathrm{exp}(|xx^{}|/l)`$\].

When the bias vanishes, the electron density $`n(x)`$ has the equilibrium form given by expression (27) with $`E_\mathrm{F}(x)=\mathrm{const}.=E_\mathrm{F}(0)`$, and we obtain a nonlinear differential equation for $`E_\mathrm{c}(x)`$. In the presence of bias, the Poisson equation (26) must be solved in conjunction with an equation for the current $`j`$. In the diffusive limit, this equation is given by the familiar drift-diffusion expression for the current,

$$j=\mu n(x)\frac{d}{dx}E_\mathrm{F}(x)=\frac{\mu }{\beta }\frac{d}{dx}n(x)+\mu n(x)\frac{d}{dx}E_\mathrm{c}(x),$$
(29)
which determines $`n(x)`$ in terms of $`E_\mathrm{c}(x)`$ and the constant parameter $`j`$. On the other hand, when the current is ballistic in an interval $`(x_{i1}^N,x_i^N)`$ \[cf. Eqs. (4)\], only the equilibrium densities $`n(x_{i1}^N),n(x_i^N)`$ at the end points of the interval enter into the description, and an averaging formalism must be provided which allows one to derive from these discrete values of the density a continuous physical density to be used in the Poisson equation.

We close this section with a brief discussion of the special case of a single barrier. In the case of a single grain boundary or a Schottky contact, the band edge profile exhibits a single peak and no valleys, so that the shape term vanishes, $`\stackrel{~}{\mathrm{\Lambda }}=0`$, and Eqs. (24) and (25) yield

$$j=ev_\mathrm{e}N_\mathrm{c}e^{\beta E_p}\frac{l}{l+\stackrel{~}{S}}(1e^{\beta eV}).$$
(30)
For a grain boundary, the barrier height $`E_\mathrm{p}`$ is given by the difference of the profile maximum at the boundary and the Fermi level in the bulk of the grain. The barrier height of a Schottky contact is equal to the difference of the profile maximum in the semiconductor and the Fermi level of the metal. Equation (30) is formally identical to Eq. (6) of Ref.  (except for the tunneling correction). However, the present derivation is different from that of Ref. , the averaging over ballistic configurations being the crucial ingredient.

If the mean free path is much longer than the reduced sample length, $`l\stackrel{~}{S}`$, one obtains from Eq. (30) the thermionic-emission formula . In the opposite case, $`l\stackrel{~}{S}`$, the transport mechanism is diffusive; with the use of

$$\mu =ev_\mathrm{e}\beta l,$$
(31)
Eq. (30) becomes

$$j=\frac{\mu N_\mathrm{c}e^{\beta E_p}}{\beta \stackrel{~}{S}}(1e^{\beta eV}).$$
(32)
Looking at the diffusive limit differentially, we have from Eq. (4) in conjunction with Eq. (27), replacing the discrete coordinate $`x_i^N`$ with the continuous coordinate $`x`$, i.e., setting $`x_i^N=il=x`$ $`(i=1,\mathrm{},N)`$, $`l=S/N`$ with $`N\mathrm{}`$,

$$j=\beta ev_\mathrm{e}N_\mathrm{c}e^{\beta [E_\mathrm{c}(x)E_\mathrm{F}(x)]}[dE_\mathrm{F}(x)/dx]l=\mu n(x)\frac{d}{dx}E_\mathrm{F}(x),$$
(33)
in agreement with Eq. (29).

### B Quantum effects

Since we are focussing attention on the case where the mean free path and the relevant structures of the band edge profile are of comparable length, we are generally dealing with systems of small dimensions and therefore must expect quantum effects such as discretization of energy states and tunneling to play a role. Considering, e.g., a potential valley with a width of the order of 20 nm, as typified by the examples discussed below, we find that the electron motion is quantized with energy spacings of about 0.03 eV. Since the barrier heights in the examples exceed this value by an order of magnitude, one may still speak of a classical continuum of states. On the other hand, the wave length of the electrons at $`T=300`$ K is $`\lambda =h/(m^{}v_\mathrm{e})10`$ nm, so that quantum tunneling should be important. The formalism for including the effect of tunneling, i.e., for going from thermionic emission to thermionic field emission, will be developed in the following. We do not include the effects of phase interference and localization, since these are not expected to play an important role for the polycrystalline materials we are considering.

The transmission probabilities for ballistic intervals with no peaks inside are treated classically, as before. Tunneling has to be taken into account near each peak in intervals $`X_n^{}<x<X_n^+`$ containing the peak at $`X_n`$ $`(n=0,1,\mathrm{},M)`$. Since we can treat only ballistic quantum transport, these intervals must not contain equilibration points. In other words, in these intervals we must effectively set $`l\mathrm{}`$, and in the integrals over $`x`$ these intervals are omitted, since here $`dx/l=0`$. The lengths to be chosen for the intervals $`[X_n^{},X_n^+]`$ will be discussed below.

In WKB approximation, the thermally averaged quantal probability $`𝒯^{\mathrm{WKB}}(i)`$ for ballistic transmission from $`x_{i1}^N`$ to $`x_i^N`$ is given by

$$𝒯^{\mathrm{WKB}}(i)=e^{\beta E_\mathrm{c}^\mathrm{m}(i)}+\beta _{E_\mathrm{c}^{(i)}}^{E_\mathrm{c}^\mathrm{m}(i)}𝑑E\mathrm{exp}\left(\beta E\frac{2}{\mathrm{}}_{y_i}^{y_i^{}}𝑑x\{2m^{}[E_\mathrm{c}(x)E]\}^{1/2}\right),$$
(34)
where $`E_\mathrm{c}^{(i)}`$ is defined after Eq. (3). The limits of integration $`y_i`$ and $`y_i^{}`$ are the turning points at energy $`E`$ on either side of the peak (if the interval $`\{i\}=[x_{i1}^N,x_i^N]`$ contains several peaks, the integral in the exponential goes from the left-most turning point to the right-most).

It is found that in the current-voltage characteristic (25), the barrier factor $`\mathrm{exp}(\beta E_\mathrm{p})`$ is to be multiplied by the tunneling correction $`𝒞^1`$, with

$$𝒞=e^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}(X_0^{})]}\left[e^{(X_M^{}X_0^+)/l}\left(\frac{1}{𝒯^{\mathrm{WKB}}(X_0^{},X_M^+)}\frac{1}{𝒯^{\mathrm{WKB}}(X_0^{},X_0^+)}\right)+\frac{1}{𝒯^{\mathrm{WKB}}(X_0^{},X_0^+)}\right],$$
(35)
where the notation $`𝒯^{\mathrm{WKB}}(X_0^{},X_M^+)`$ refers to the averaged WKB transmission probability $`𝒯^{\mathrm{WKB}}(i)`$ for the interval $`[X_0^{},X_M^+]`$, etc; here, $`X_0`$ is the position of the overall maximum peak $`E_\mathrm{c}^\mathrm{m}`$. The reduced sample length $`\stackrel{~}{S}`$ and the shape term $`\stackrel{~}{\mathrm{\Lambda }}`$ that enter the effective transport length $`L`$ \[cf. Eq. (24)\] now appear as

$$\stackrel{~}{S}=𝒞^1_0^S^{}𝑑xe^{\beta [E_\mathrm{c}^\mathrm{m}E_\mathrm{c}(x)]},$$
(36)
where the upper limit $`S^{}`$ implies that all intervals $`[X_n^{},X_n^+]`$ $`(n=0,1,\mathrm{},M)`$ are to be omitted, and

$$\stackrel{~}{\mathrm{\Lambda }}=𝒞^1\underset{v=1}{\overset{M}{}}_{X_v^{}}^{X_v^{}}𝑑xe^{|xx^{}|/l}e^{\beta E_\mathrm{c}^\mathrm{m}}\left[A_ve^{\beta E_\mathrm{c}(X_v)}e^{\beta E_\mathrm{c}(x)}\right],$$
(37)
with $`X_v^{}=\mathrm{max}\{X_v^{},X_{v1}^+\}`$ and

$$A_v=𝒯(X_v^{},X_v^+)/𝒯^{\mathrm{WKB}}(X_v^{},X_v^+),v=1,\mathrm{},M,$$
(38)
where $`𝒯`$ is the average classical transmission probability (3). It can be shown that $`\stackrel{~}{\mathrm{\Lambda }}<S`$, as in the classical case.

For a single barrier, Eq. (30) is generalized to

$$j=ev_\mathrm{e}N_\mathrm{c}𝒞^1e^{\beta E_p}\frac{l}{l+\stackrel{~}{S}}(1e^{\beta eV}).$$
(39)
According to Eq. (36), $`\stackrel{~}{S}`$ includes the tunneling correction factor $`𝒞^11`$, and thus tunneling enhances the relative effect of the non-ballistic part of the electron motion embodied in the term $`\stackrel{~}{S}`$ in the denominator of expression (39).

The intervals $`[X_n^{},X_n^+]`$ enclosing the peaks at $`X_n`$ are defined as the intervals in which tunneling plays a role; they are determined by the requirement that the ratio $`A_v`$ becomes virtually independent of the interval if that extends beyond the end points $`X_n^\pm `$. On the other hand, it must be ascertained that these lengths are smaller than the mean free path $`l`$, otherwise the quantum correction scheme breaks down: if tunneling takes place over distances larger than the mean free path, thermalization and tunneling occur simultaneously, which cannot be described in the present framework. Explicit calculations of the quantum corrections will be carried out below.

### C The degenerate case

In the degenerate case, a simple treatment is possible only in the limit of zero bias. Formula (2) for the current is to be replaced (for infinitesimal bias) with

$$j(i)=\frac{4\pi em^{}}{\beta h^3}\delta _i\frac{}{E_\mathrm{F}}_{E_\mathrm{c}^{(i)}}^{\mathrm{}}𝑑ET_i(E)\mathrm{ln}(1+e^{\beta [EE_\mathrm{F}]}),$$
(40)
where we have set $`E_\mathrm{F}(x_{i1}^N)=E_\mathrm{F}`$ and $`E_\mathrm{F}(x_i^N)=E_\mathrm{F}+\delta _i`$. Classically, this becomes

$$j(i)=\frac{4\pi em^{}}{\beta h^3}\delta _i\mathrm{ln}(1+e^{\beta [E_\mathrm{c}^\mathrm{m}(i)E_\mathrm{F}]}).$$
(41)
By analogy with Eq. (6), we then find

$$E_\mathrm{F}(S)E_\mathrm{F}(0)=\underset{i=1}{\overset{N}{}}\delta _i=j\frac{\beta h^3}{4\pi em^{}}\underset{i=1}{\overset{N}{}}\frac{1}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}(i)]})},$$
(42)
with $`E_\mathrm{F}(0)`$ and $`E_\mathrm{F}(S)`$ differing infinitesimally from the equilibrium value $`E_\mathrm{F}`$. Denoting here the average over the sum (cf. Sec. II.A), multiplied by $`\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})`$, by $`\mathrm{\Xi }_\mathrm{d}`$,

$$\mathrm{\Xi }_\mathrm{d}=\underset{i=1}{\overset{N}{}}\frac{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}(i)]})}_{\{N,x_i^N\}},$$
(43)
we have

$$eV=E_\mathrm{F}(S)E_\mathrm{F}(0)=j\frac{\beta h^3}{4\pi em^{}}\frac{1}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})}\mathrm{\Xi }_\mathrm{d}.$$
(44)
The calculation of the average sum $`\mathrm{\Xi }_\mathrm{d}`$ follows Sec. II.B. A (classical) effective transport length $`L_\mathrm{d}`$ is introduced as

$$L_\mathrm{d}=\mathrm{\Xi }_\mathrm{d}l=l+\stackrel{~}{S}_\mathrm{d}+\stackrel{~}{\mathrm{\Lambda }}_\mathrm{d},$$
(45)
where

$$\stackrel{~}{S}_\mathrm{d}=_0^S𝑑x\frac{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}(x)]})}$$
(46)
is the reduced sample length for the degenerate case, in generalization of Eq. (16), and

$$\stackrel{~}{\mathrm{\Lambda }}_\mathrm{d}=\underset{v=1}{\overset{M}{}}_{X_v^{}}^{X_v}𝑑xe^{|xx_v^{}|/l}\left[\frac{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}(X_v)]})}\frac{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}^\mathrm{m}]})}{\mathrm{ln}(1+e^{\beta [E_\mathrm{F}E_\mathrm{c}(x)]})}\right]$$
(47)
is the generalization of the shape term (23). The zero-bias conductance per unit area, finally, is obtained as

$$g=\left(\frac{|j|}{V}\right)_{V0}=\frac{4\pi e^2m^{}}{\beta h^3}\mathrm{ln}(1+e^{\beta E_\mathrm{p}})\frac{l}{L_\mathrm{d}},$$
(48)
with $`E_\mathrm{p}=E_\mathrm{c}^\mathrm{m}E_\mathrm{F}`$ (note that in the degenerate case, $`E_\mathrm{p}`$ may be negative). Quantum effects may be taken into account as in the nondegenerate case.

### D The effect of dimensionality

The samples we consider are assumed to have a parallel-plane structure and thus have an essentially one-dimensional geometry. Nevertheless, the treatment of the transport process itself should, of course, be three-dimensional. Therefore, in the discussion preceding Eq. (9), one must consider the distance between collisions, $`\xi `$, in three-dimensional space. This introduces a polar angle to be summed over appropriately in averaging over the ballistic configurations, thereby rendering the formalism appreciably more complicated. In our effort to obtain a simple, closed formula for the current-voltage characteristic, we have restricted ourselves to a one-dimensional formulation, which leads to the desired result in a straightforward way.

Now, for the special case of a constant profile, $`E_\mathrm{c}(x)=0`$, de Jong  has derived a formula which describes the transition from the (ballistic) Sharvin resistance  to the (diffusive) Drude zero-bias conductance . In this work, use is made of an integro-differential equation in two and three dimensions, leading to a numerical result which, for the three-dimensional case, is summarized in the formula (in the notation of our Eq. (48) with $`E_\mathrm{c}^\mathrm{m}=0`$ and $`\beta E_\mathrm{F}1`$)

$$g=\frac{4\pi e^2m^{}E_\mathrm{F}}{h^3}\frac{l}{l+\frac{3}{4}\gamma S},$$
(49)
where $`\gamma `$ increases monotonically from 1 to $`4/3`$ as $`l/S`$ goes from 0 (diffusive limit) to $`\mathrm{}`$ (ballistic limit). In our one-dimensional formulation, the denominator in formula (49) reads simply $`l+S`$. We therefore suggest that the restriction to a one-dimensional formulation introduces a numerical error of perhaps 30 percent; the main features of our model, which the following examples show to involve enhancements by factors of 10, should not be severely affected.

Unfortunately, one cannot make use of differential equations in the more general case when the profile $`E_\mathrm{c}(x)`$ changes significantly over distances of the order of the mean free path $`l`$. Anyhow, we are not so much interested in the numerical solution of the transport problem (which would most efficiently be handled by Monte Carlo simulations) but, as far as possible, in its physical analysis via simple and transparent closed formulas.

## IV Examples

### A Zero-bias conductivity of a chain of identical grains

The zero-bias conductance per unit area, $`g=(|j|/V)_{V0}`$, is obtained as

$$g=\beta e^2v_\mathrm{e}N_\mathrm{c}𝒞^1e^{\beta E_\mathrm{p}}\frac{l}{L}=\frac{4\pi e^2m^{}}{\beta h^3}𝒞^1e^{\beta E_\mathrm{p}}\frac{l}{L}.$$
(50)
The band edge profile $`E_\mathrm{c}(x)`$ for zero bias is given by its equilibrium shape, and is calculated as a solution of the Poisson equation (26) in the trapping model.

We consider a chain of $`\nu `$ identical grains, each of length $`s`$, as shown in Fig. 3. There are $`\nu 1`$ identical valleys in $`E_\mathrm{c}(x)`$. Writing $`\stackrel{~}{S}=\nu \stackrel{~}{s}`$ and $`\stackrel{~}{\mathrm{\Lambda }}=(\nu 1)\stackrel{~}{l}`$, we have from Eq. (24)

$$L=l+\nu \stackrel{~}{s}+(\nu 1)\stackrel{~}{l}.$$
(51)
As mentioned above, the profile $`E_\mathrm{c}(x)`$, and therefore also the barrier height $`E_\mathrm{p}`$, the reduced grain length $`\stackrel{~}{s}`$, and the single-grain shape term $`\stackrel{~}{l}`$, indirectly depend on the mean free path $`l`$ via its connection with the donor density $`N_{\mathrm{don}}`$. The $`l`$-dependence of the main feature of the profile, the barrier height $`E_\mathrm{p}`$, can be read from the $`l`$-dependence of the conductance $`g`$ for a single grain in the ballistic regime, when $`L=l`$ in Eq. (50).

The term $`l`$ in expression (51) for the effective transport length $`L`$ represents the ballistic contribution to the current. For purely ballistic motion ($`l\nu s`$ and $`Ll`$), one finds from Eq. (50) in the classical limit ($`𝒞=1`$) that only one barrier, the front barrier, is relevant since it eclipses all others (cf. above, and also the discussion in Sec. II of Ref. ). However, when tunneling takes place (possibly through several neighboring peaks), Eq. (39) in conjunction with Eq. (35) is to be used to obtain the conductance.

For the purpose of illustration, we consider two silicon samples with grain length $`s=30`$ nm ($`\mu `$c-Si) and $`s=100`$ nm (pc-Si), respectively. Instead of the zero-bias conductance $`g`$, we introduce here the zero-bias conductivity $`\sigma `$ as conductance times sample length,

$$\sigma =gS=g\nu s$$
(52)
(in the diffusive limit, $`\sigma `$ is independent of the number of grains $`\nu `$). The conductivity has been calculated at temperature $`T=300`$ K by means of formulas (50) and (51) as a function of the donor density $`N_{\mathrm{don}}`$. Applying the criteria discussed in the final paragraph of Sec. III.B, the length of the “tunneling intervals” $`[X_n^{},X_n^+]`$ enclosing the peaks was taken to be 6 nm (which, not surprisingly, is of the order of the wave length $`\lambda =10`$ nm of the electrons); this value is much smaller than the magnitude of the mean free path in all cases considered. The results are shown in Fig. 4 as a function of the mean free path $`l`$, employing the connection between $`l`$ and $`N_{\mathrm{don}}`$ obtained from Ref.  and displayed in the inset. It is seen that the conductivity depends appreciably on the number of grains in the case of the smaller grain size, $`s=30`$ nm. Thus it emerges that the conductivity calculated for a single grain cannot simply be carried over to the entire microcrystalline sample. The latter must be considered as a whole; there is in this case no grain-specific conductivity.

Tunneling has a direct influence on the barrier transmission probability, which is taken into account through the correction factor $`𝒞^1`$ in Eq. (50). It enhances the transmission probability by up to 50% in the region of small $`l`$.

In Fig. 5, we summarize the results of the unified model in comparison to those of the drift-diffusion and thermionic-emission models. Since tunneling does not affect appreciably the mutual relation between the different transport models, we here consider only the classical conductivities, and plot these relative to the conductivity within the drift-diffusion model, $`\sigma _{\mathrm{DD}}`$ \[with $`L=\nu \stackrel{~}{s}`$ in Eq. (50)\]. The curves labelled UM(1) and UM(100) represent the conductivity of the unified model for a chain of one and a hundred grains, respectively, divided by the conductivity calculated within the drift-diffusion model. In the regions where these curves approach unity, the transport mechanism is predominantly diffusive. The curve labelled TE (“thermionic emission”) represents the relative conductivity for purely ballistic transport across a single grain boundary, the result being identified (as is usually done) with the conductivity of the entire chain. This procedure ignores the eclipsing effect alluded to above, and is justified only if the mean free path is long compared to the width of the barrier but short compared to the length of the grain \[cf. the conditions leading to Eq. (21)\], so that while moving through the grain, the electrons are thermalized and “face” each grain boundary barrier with the same thermal distribution as when passing over the previous one.

We see that the transport mechanism tends to become diffusive for very small values of $`l`$, and also for $`l>80`$ nm in the case $`\nu =100`$; this holds for $`s=30`$ nm as well as for $`s=100`$ nm. The thermionic-emission model yields acceptable results in the region $`20<l<60`$ nm at $`s=100`$ nm for $`\nu =1`$ and $`\nu =100`$. At $`s=30`$ nm, it is valid for $`\nu =1`$ but completely invalid for $`\nu =100`$. In the latter case, neither the drift-diffusion nor the thermionic emission models describe adequately the correct mechanism \[which is represented by the curve labelled UM(100)\].

The transport properties have been discussed here for just two grain lengths $`s`$ representative of microcrystalline and polycrystalline silicon, respectively. A more comprehensive study would have to deal with the $`s`$-dependence over a suitably broad range, which in particular may lead to the disclosure of possible scaling properties.

### B Degenerate case: Single barrier

We apply formula (48) to transport through a single grain boundary. Choosing parameter values so as to reproduce approximately the conditions of the example of Ref. , we consider the temperature dependence of the conductance for a grain boundary barrier in highly doped pc-SnO<sub>2</sub>:Sb with grain length $`s=50`$ nm. We have calculated the equilibrium band edge profile $`E_\mathrm{c}(x)`$ at $`T=300`$ K and $`N_{\mathrm{don}}=7.2\times 10^{18}`$ cm<sup>-3</sup>, corresponding to a mean free path $`l=11`$ nm. We assume a single trapping level at midgap (1.75 eV above the valance band edge) with trapping state density $`N_\mathrm{t}=1.95\times 10^{12}`$ cm<sup>-2</sup>. The barrier height is obtained as $`E_\mathrm{p}=0.038`$ eV and the barrier width as $`6`$ nm. Since we intend to apply formula (48) in a schematic manner only and the band edge profile is found to depend only weakly on $`T`$ and $`N_{\mathrm{don}}`$ (or $`E_\mathrm{F}`$), we adopt the profile calculated at $`T=300`$ K for all values of $`T`$ and control the degree of degeneracy by independently choosing the value of $`E_\mathrm{F}`$ in Eq. (48).

In Fig. 6, we display the $`T`$-dependence of the barrier conductivity $`\sigma =gS`$, calculated from Eq. (48) using for the mean free path the fixed value $`l=11`$ nm (when comparing with the results of Ref. , one must take account of the factor $`\alpha _{\mathrm{eff}}10^2`$ introduced there). The case considered here \[$`E_\mathrm{F}=3.52`$ eV, compared to $`E_\mathrm{c}`$(grain bulk) = 3.50 eV\] is strongly degenerate; nevertheless, the results of calculations using Boltzmann and Fermi-Dirac statistics \[UM(non-d) vs. UM(d)\] are not too far apart. Further, it is observed, by comparing the curves labelled UM(d) and UM(d,cl), that the effect of tunneling increases the conductivity by more than a factor of 2, becoming stronger as the temperature decreases.

The purely diffusive and ballistic (degenerate) conductivities are also shown in Fig. 6. It appears that, as the temperature rises, the transport character in the unified model changes from ballistic to diffusive. This is governed by the relative size of the terms $`l`$ and $`\stackrel{~}{S}_\mathrm{d}`$ in the effective transport length $`L_\mathrm{d}`$ appearing in the denominator of expression (48) for the conductance $`g`$.

Formula (46) yields for $`\stackrel{~}{S}_\mathrm{d}`$ a value which increases with $`E_\mathrm{F}`$, i.e., with donor density $`N_{\mathrm{don}}`$. In Ref. , the corresponding term $`\frac{3}{4}w`$ is found (by fitting to data) to decrease instead; a more detailed analysis appears to be necessary for an explanation of this discrepancy.

## V Summary and conclusions

For electron transport in parallel-plane semiconducting structures, we have developed a generalized Drude model which unifies ballistic and diffusive transport for arbitrary magnitude of the mean free path and arbitrary shape of the conduction band edge profile. The semiclassical approach has been adopted, but tunneling has been taken into account in WKB approximation.

The basic assumption of the model is that the electrons move ballistically over intervals whose lengths are randomly distributed about the value of the mean free path. By averaging over the random configurations of ballistic intervals, we have derived simple formulas for the current-voltage characteristic (in the nondegenerate case) and for the zero-bias conductance (in the degenerate case). The distinctive feature of these formulas is the presence of an effective length that comprises a shape term directly manifesting the interplay of ballistic and diffusive transport. Previously obtained formulas for the current-voltage characteristic and for the zero-bias conductance refer to special cases and do not include such a term.

We have performed numerical calculations of the zero-bias conductivity for chains of grains of (nondegenerate) $`\mu `$c-Si and pc-Si, and for a single grain boundary in highly doped (degenerate) pc-SnO<sub>2</sub>:Sb. The calculations for Si show substantial deviations of the results of the unified model from those of the purely ballistic and purely diffusive models. Moreover, within the unified model, one finds a fairly strong dependence of the conductivity on the number of grains.

For the calculation of the zero-bias conductivity, the band edge profile to be used is the equilibrium profile. Except in this case and in the diffusive limit, the determination of the band edge profile is highly complicated in general. Basically, one has to solve the Poisson equation along with the relevant current equation self-consistently, taking into account the averaging of the electron density over configurations of ballistic intervals.

In this work, we have considered transport in one dimension; it has been argued that this should be sufficient to exhibit the essential features of the physical phenomena involved. Possible generalizations would be the inclusion of the coupling to minority carriers, of optically induced carrier generation, and of recombination.


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# Effective Area-Elasticity and Tension of Micro-manipulated Membranes

\[

## Abstract

We evaluate the effective Hamiltonian governing, at the optically resolved scale, the elastic properties of micro-manipulated membranes. We identify floppy, entropic-tense and stretched-tense regimes, representing different behaviors of the effective area-elasticity of the membrane. The corresponding effective tension depends on the microscopic parameters (total area, bending rigidity) and on the optically visible area, which is controlled by the imposed external constraints. We successfully compare our predictions with recent data on micropipette experiments.

\]

Micro-manipulation techniques, where, e.g., magnetic or optical traps pull on micrometric beads attached to a material, are increasingly used to probe the elastic response of various soft-matter systems, such as biological polymers (e.g., DNA  or proteins ), phase boundaries of Langmuir monolayers , surfactant vesicles  and even living cells . Combined with optical observations, these techniques should allow in the future to finely test the elastic theories of complex systems, e.g, by monitoring the shape and fluctuations of a system while imposing inhomogeneous boundary conditions. Although surfactant membranes and vesicles  are apparently one of the simplest system, there is still some confusion regarding the appropriate Hamiltonian describing their elasticity, and in particular about the role and value of an effective tension $`\sigma `$. The latter is not a well-identified microscopic quantity, contrary to the bending rigidity $`\kappa `$. In different thermodynamic ensembles , various approaches have been proposed: phenomenological self-consistent theories , approximations involving Lagrange multipliers , or formal renormalization schemes . In this Letter, we propose an approach based on a large but finite coarse-graining , devised for the interpretation of measurements combining micro-manipulation and optical observations.

Fluid membranes in aqueous solutions often consist of a fixed number of highly insoluble lipid or surfactant molecules. Since stretching a flat membrane involves very high energies, while macroscopically bending it involves energies of order $`k_\mathrm{B}T`$, membranes are commonly modeled as fluctuating two-dimensional sheets with a prescribed microscopic area $`\overline{A}`$ and a curvature elasticity . At the macroscopic scale, membranes actually appear very different: their optically visible area $`A`$ fluctuates about some value depending on the temperature and on the external constraints. Part of the total area $`\overline{A}`$ is stored in short scale fluctuations that are optically unresolved . For such a critically fluctuating system, a coarse-grained effective Hamiltonian $`_{\mathrm{eff}}`$, integrating all sub-optical details, is clearly more adequate than the microscopic Hamiltonian.

Our goal is to calculate this effective macroscopic Hamiltonian $`_{\mathrm{eff}}`$ and to investigate the associated area-elasticity and tension. We start by considering a quasi-planar membrane with a fixed microscopic area $`\overline{A}`$, which is attached to a fixed frame of area $`L^2`$. We choose the simplest microscopic curvature Hamiltonian: the lowest-order, quadratic approximation of the Canham-Helfrich Hamiltonian :

$$_c[h_m]=d^2x\frac{\kappa }{2}\left(^2h_m\right)^2.$$
(1)
Here $`h_m(𝐱)`$ is the height of the membrane above a reference plane (Monge gauge), as resolved microscopically. We then determine the coarse-grained Hamiltonian $`_{\mathrm{eff}}[h]`$, where $`h(𝐱)`$ is the height of the membrane as resolved optically. This Hamiltonian is such that $`\mathrm{exp}(\beta _{\mathrm{eff}}[h])`$ gives the probability for the occurrence of any optically visible membrane shape $`h`$, whatever its fluctuating microscopic detail. Technically, this is a one-step renormalization of the fixed area constraint.

We find that $`_{\mathrm{eff}}`$ involves a non-linear area-elasticity energy $`_s(A)`$ for the coarse-grained, optically visible, area $`A`$. This is the effective potential which is probed by pulling a membrane in an optically resolved micro-manipulation. Depending on the microscopic excess area $`\alpha _m=(\overline{A}L^2)/L^2`$ and on the constraints exerted on the membrane, we find three distinct regimes: a floppy regime, an entropic-tense regime, and a stretched-tense regime. We provide explicit formulae for the effective tension $`\sigma (A)d_s/dA`$ in these three regimes. To better describe the tense regime, we further incorporate a microscopic stretching elasticity. We then contrast our approach and the resulting picture with the common use of a heuristic tension proposed by Helfrich and Servuss . Eventually, we point out that our results can be applied to giant vesicles with a fixed volume $`V_0=\frac{4}{3}\pi R_0^3`$, by taking $`L^2=4\pi R_0^2`$. This allows us to perform a first test of our theory: re-analyzing the micro-pipette experiments of Evans and Rawicz , we find an excellent fit for the cross-over between the entropic-tense and the stretched-tense regimes. Finally, we point out the approximations involved in our calculations and we propose several possible experiments.

The thermal fluctuations of a membrane of fixed microscopic area $`\overline{A}d^2x(1+\frac{1}{2}\left(h_m\right)^2)`$ are described by the partition function

$$Z=𝒟[h_m]\delta \left(L^2+d^2x\frac{1}{2}\left(h_m\right)^2\overline{A}\right)e^{\beta _c}.$$
(2)
We perform the decomposition $`h_m(𝐱)=h(𝐱)+h^>(𝐱)`$, in which $`h(𝐱)`$ (in gray in Fig. 1) has wavevectors in the range $`0<q<\mathrm{\Lambda }`$, where $`\mathrm{\Lambda }`$ corresponds to the experimental limit of resolution, e.g., optical, and $`h^>(𝐱)`$ has wavevectors in the range $`\mathrm{\Lambda }<q<\mathrm{\Lambda }_0`$, where $`\mathrm{\Lambda }_0`$ is a molecular cutoff. Splitting the integration as $`𝒟[h_m]=𝒟[h]𝒟[h^>]`$, and writing the delta-function in Fourier space, we can rewrite Eq. (2) as

$$Z=𝒟[h]\mathrm{exp}\left\{\beta \left[_c[h]+_s(A)\right]\right\}$$
(3)
where $`A[h]=L^2+d^2x\frac{1}{2}\left(h\right)^2`$ is the optically visible area, and

$`_s(A)={\displaystyle \frac{1}{\beta }}\mathrm{ln}{\displaystyle _i\mathrm{}^i\mathrm{}}𝑑\lambda `$ $`\mathrm{exp}[\lambda (\overline{A}A)`$ (5)
$`{\displaystyle \frac{L^2}{2}}{\displaystyle _{𝐪^>}}\mathrm{ln}(\beta \kappa q^4\lambda q^2)].`$
This defines the effective Hamiltonian at the optical scale $`_{\mathrm{eff}}[h]=_c[h]+_s(A[h])`$. In the thermodynamic limit, the above integral can be evaluated at the saddle point:

$$_s(A)\frac{\lambda _s}{\beta }\left(\overline{A}A\right)+\frac{L^2}{2\beta }_{𝐪^>}\mathrm{ln}\left(\beta \kappa q^4\lambda _sq^2\right),$$
(6)
with $`\lambda _s`$ the solution of $`\overline{A}A=\frac{1}{2}L^2_{𝐪^>}(\beta \kappa q^2\lambda _s)^1`$. The effective tension for an optical area $`A`$, $`\sigma (A)d_s/dA=\lambda _s/\beta `$, is thus related to the area stored in the sub-optical modes by:

$$\frac{\overline{A}A}{L^2}\frac{1}{8\pi \beta \kappa }\mathrm{ln}\frac{\kappa \mathrm{\Lambda }_0^2+\sigma }{\kappa \mathrm{\Lambda }^2+\sigma }.$$
(7)
Integrating, we obtain an explicit formula for the surface potential (see Fig. 2):

$$_s(A)=\frac{L^2\mathrm{\Lambda }_0^2}{8\pi \beta }\left[\left(\frac{\mathrm{\Lambda }^2}{\mathrm{\Lambda }_0^2}1\right)\mathrm{ln}\left(e^X1\right)+X\right],$$
(8)
where $`X=8\pi \beta \kappa (\overline{A}A)/L^2`$. $`_s(A)`$ has a minimum for

$$A^{}=\overline{A}\frac{L^2}{4\pi \beta \kappa }\mathrm{ln}\frac{\mathrm{\Lambda }_0}{\mathrm{\Lambda }},$$
(9)
at which the tension $`\sigma `$ vanishes. For $`A<A^{}`$, the tension saturates to the negative value $`\sigma \kappa \mathrm{\Lambda }^2`$, while for $`A\overline{A}^{}`$ it diverges as $`\sigma (\mathrm{\Lambda }_0^2L^2)/[8\pi \beta (\overline{A}A)]`$, as a consequence of the prescribed microscopic area $`\overline{A}`$.

Floppy and tense regimes. – A crucial remark is that the optical area $`A`$ cannot be smaller than the frame area $`L^2`$, which results in two possibilities (Fig. 2). If the microscopic excess area $`\alpha _m=(\overline{A}L^2)/L^2`$ is larger than

$$\alpha _m^c=\frac{1}{4\pi \beta \kappa }\mathrm{ln}\frac{\mathrm{\Lambda }_0}{\mathrm{\Lambda }},$$
(10)
we have $`A^{}>L^2`$ and the minimum of $`_s(A)`$ is indeed physically realizable \[Fig. 2 $`(a_1)`$\]. The coarse-grained unperturbed membrane is then in a floppy state \[Fig. 1 $`(a_1)`$\], in which the tension has a vanishing optimal value.

Conversely, if the attachment to the frame results in $`\alpha _m<\alpha _m^c`$, the unphysical hatched region of Fig. 2 comes to the right of the minimum, and the zero-tension state is no longer accessible. The unperturbed coarse-grained membrane finds then its minimum energy in a tense, optically flat state, with $`A=L^2`$ \[see Figs. 2 $`(b_1)`$ and 1 $`(b_1)`$\]. Two tense regimes are however possible: (i) when $`\kappa \mathrm{\Lambda }^2\sigma \kappa \mathrm{\Lambda }_0^2`$, the membrane is in an entropic-tense state with (still in the flat state):

$$\sigma _0\kappa \mathrm{\Lambda }_0^2\mathrm{exp}\left(8\pi \beta \kappa \alpha _m\right),$$
(11)
according to Eq. (7). While $`\kappa \mathrm{\Lambda }_0^2`$ compares with ordinary liquids tensions, the exponential reduction factor in Eq. (11) leads to extraordinary small values of membrane tensions, in line with many observations . (ii) When $`\sigma `$ compares with $`\kappa \mathrm{\Lambda }_0^2`$, due to the smallness of $`\alpha _m`$, the membrane is in a stretched-tense regime, where the tension describes the divergence of $`_s`$ for $`A\overline{A}^{}`$, i.e., $`\sigma \mathrm{\Lambda }_0^2/(8\pi \beta \alpha _m)`$. (This behavior will be corrected next by the introduction of a microscopic streching elasticity.) A remarkable point is that in the tense states, $`\sigma `$ is independent of the coarse-graining scale, $`\mathrm{\Lambda }`$. Besides, since $`\alpha _m<\alpha _m^c`$, the characteristic length $`(\kappa /\sigma )^{1/2}`$ is always smaller than the optical cutoff, $`\mathrm{\Lambda }^1`$, thus the bending rigidity is masked by the effective tension.

If now the membrane is stretched by external means, the typical value of $`A`$ is increased compared to its free value ($`A^{}`$ or $`L^2`$), and the system can be brought into tenser regimes. The response to weak perturbations of an initially floppy membrane \[$`\alpha _m>\alpha _m^c`$, Figs. 1 $`(a_1)`$ and 2 $`(a_1)`$\] is described, from Eq. (8), by a quadratic elasticity around the minimum $`A^{}`$:

$$_s(A)\frac{1}{2}k_{\mathrm{eff}}L^2\left(\frac{AA^{}}{L^2}\right)^2,k_{\mathrm{eff}}=8\pi \beta \kappa ^2\mathrm{\Lambda }^2,$$
(12)
Under stronger stretching, the membrane reaches an entropic-tense state \[Figs. 1$`(a_2)`$ and 2$`(a_2)`$\]. Its effective elasticity is then similar to that of an initially tense membrane. According to Eq. (7), the tension is given by

$$\sigma \sigma _0\mathrm{exp}\left(8\pi \beta \kappa \alpha \right),$$
(13)
where $`\alpha =(AL^2)/L^2`$ is the apparent excess area. Eventually, further pulling brings the membrane into the stretched-tense regime with $`\sigma \mathrm{\Lambda }_0^2/[8\pi \beta (\alpha _m\alpha )]`$.

Including Stretching Elasticity. – A better description of a strongly stretched membrane can actually be achieved by taking into account the small but finite extensibility at microscopic scales. We remove the delta-function in Eq. (2), and replace the Hamiltonian by

$$_c+\frac{k_m}{2\overline{A}}\left[L^2+d^2x\frac{1}{2}\left(h_m\right)^2\overline{A}\right]^2.$$
(14)
Applying a Hubbard-Stratonovich transformation , we obtain Eq. (5) with an additive correction $`\frac{1}{2}(\overline{A}/\beta k_m)\lambda ^2`$ in the exponential. Thus, instead of Eq. (7), the saddle-point equation becomes (with $`\sigma =\lambda _s/\beta `$):

$$\overline{A}\left(1+\frac{\sigma }{k_m}\right)A=\frac{L^2}{8\pi \beta \kappa }\mathrm{ln}\frac{\kappa \mathrm{\Lambda }_0^2+\sigma }{\kappa \mathrm{\Lambda }^2+\sigma }.$$
(15)
Integrating this equation leads to an improved form for $`_s(A)`$. Clearly, as long as $`\sigma k_m`$, Eqs. (7) and (15) are equivalent. The present correction is useful only to describe the cross-over to and the tense-stretched regime \[$`\sigma `$ comparable to or larger than $`\mathrm{min}(k_m,\kappa \mathrm{\Lambda }_0^2)`$\], when it modifies the divergence of $`_s`$ for large values of $`A`$.

Comparison with the model of Helfrich and Servuss. – In Ref. , the membrane is macroscopically depicted as a flat surface ($`AL^2`$), and $`\sigma `$ is introduced as a microscopic surface tension, which is self-consistently determined by prescribing the average value of the fluctuating microscopic excess-area (in the ensemble in which the frame is fixed). Then the contribution of the stretching elasticity is added by hand. In our theory, we take into account the actual microscopic membrane elasticity, and we define the effective tension $`\sigma (A)`$ as the derivative of the area elasticity $`_s(A)`$ associated with the coarse-grained membrane area $`A`$. Although Eqs. (7) and (15) are very similar to those derived in Ref. , our clear distinction between $`L^2`$, $`A`$ and $`\overline{A}`$, naturally allows to describe the area elasticity of a membrane deformed by external actions (while the description of Ref.  allows no distinction between $`A`$ and $`L^2`$).

Quasi-spherical vesicles. – Let us now briefly discuss the case of a quasi-spherical vesicle with a fixed volume $`V_0=\frac{4}{3}\pi R_0^3`$. Parameterizing its shape by $`R(\theta ,\varphi )=R_0[1+_\mathrm{}mu_\mathrm{}mY_\mathrm{}m(\theta ,\varphi )]`$ and taking into account the volume constraint $`\sqrt{4\pi }u_{0,0}=_{\mathrm{}>0,m}|u_\mathrm{}m|^2`$, the microscopic area is fixed, in the partition function, by the factor (see, e.g., ):

$$\delta \left(4\pi R_0^2+R_0^2\underset{\mathrm{}2,m}{}\frac{1}{2}(\mathrm{}1)(\mathrm{}+2)|u_\mathrm{}m|^2\overline{A}\right).$$
(16)
Comparing with the delta-function in Eq. (2), we see that the area $`4\pi R_0^2`$ plays the role of the frame area $`L^2`$. It will be shown in detail elsewhere that a coarse-graining procedure yields the same results as in the flat case, provided the vesicle is large enough for the optical wavelength to corresponds to quasi-planar modes. At the optical resolution, the vesicle still has a prescribed volume $`V_0`$ (the volume is almost unaffected by quasi-planar modes), and is described by the effective Hamiltonian $`_{\mathrm{eff}}`$ obtained previously, upon replacement of $`L^2`$ by $`4\pi R_0^2`$.

To check our model, we have re-analyzed the most recent micropipette experiments : a certain amount of membrane area, initially invisible at the optical resolution, is aspirated from a vesicle my means of a pressurized micropipette. The induced tension $`\sigma `$, obtained from Laplace’s law, is measured as a function of the variation of the apparent area. Our Eq. (15) can be rewritten in the tense regime as

$$\alpha =C_1+\left(8\pi \beta \kappa \right)^1\mathrm{ln}\sigma +C_3\frac{\sigma }{k_m},$$
(17)
with $`C_1=\alpha _m(8\pi \beta \kappa )^1\mathrm{ln}(\kappa \mathrm{\Lambda }_0^2)`$ and $`C_3=1+\alpha _m`$. As shown in Fig. 3, this yields a nice fit with $`C_1\alpha _0=0.0258\pm 0.0003`$ (with $`\alpha _0`$ the unknown expansion at lowest pressure ), $`\beta \kappa =10.7\pm 0.3`$, and $`k_m/C_3=183\pm 6\mathrm{erg}/\mathrm{cm}^2`$. The slope in the linear low tension regime precisely determines $`\beta \kappa `$. The value of $`C_1`$ is hard to interpret, since $`\alpha _0`$ and $`\alpha _m`$ are unknown. An estimate of $`k_m`$ can be obtained by assuming $`\alpha _m0.05`$ (the range of the area expansion variation); this yields $`k_m192\mathrm{erg}/\mathrm{cm}^2`$. In Ref. , the data was also nicely fitted with Helfrich’s formula , since it equally leads to Eq. (17) in the tense regime, however with different definitions for $`C_1`$ and $`C_3`$. These differences affect the determination of $`k_m`$, since $`C_3=1`$ in Helfrich’s theory.

Conclusion. – Starting from a clearly defined picture at the microscopic scale (an almost incompressible membrane built of a fixed number of lipids, attached to a fixed frame, or enclosing a quasi-spherical volume), we have derived an explicit Hamiltonian $`_{\mathrm{eff}}[h]`$ describing the elasticity of a membrane, as gauged by its optically resolved shape $`h`$. This effective description allows, in theory, to determine the response to an external perturbation described by a Hamiltonian $`_{\mathrm{ext}}[h]`$, e.g., to a set of pulling micron-size beads. Our formulae for the effective tension in the stretched states resemble those of Ref. , but our formalism offers a clearer definition, a wider applicability, and basically a justification of the concept of effective tension. This will allow us to emphasize elsewhere the distinction between the effective membrane tension and the mechanical frame tension $`\mathrm{\Sigma }=\beta ^1d(\mathrm{ln}𝒵)/dL^2`$.

We have kept throughout the description at the Gaussian, quadratic level (neglecting renormalization of the bending rigidities and associated effects), however we believe that our results in their present form offer a reasonably simple frame for the analysis of experiments, including new micro-manipulation studies.

We thank D. Bartolo and C. Tordeux for illuminating discussions. LP acknowledges the support of the CNRS.