NmoStructured Materials. Vol. 6. pp. 755-758.1995 Copyright Q 1995 Elsevier Science Ltd Printed in the USA.

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SPECIFIC

HEAT

OF NANOSTRUCTURED
R. Pirc
61111 Ljubljana, Slovenia

MATERIALS

J. Stefan Institute, Universitst des Saarlandes,

A. Hole
66041 Saarbriicken, Germany

Abstract - We study the thermal properties of nanostructured materials assuming that a sizable fraction of atoms in the intercrystalline boundary region move in local bistable soft potentials. The extra degrees of freedom aTe represented by a set of twolevel systems. The effects of disorder are described by local Gaussian random energies representing the asymmetry of the soft potentials, and by random finite-range pairwise interactions. Using the pseudospin formalism and the replica method known from the theory of dipolar glasses, the internal energy and the excess specific heat are evaluated. It is shown that in the replica symmetric case, corresponding to a mean field approximation, the excess specific heat is linear at low temperatures and goes through a broad maximum at higher temperatures. INTRODUCTION
One of the main characteristics of nanostructured materials (NSM S) is the existence of a disordered boundary region between the nanosized microcrystallites, which may contain up to 50% of all the atoms (1,2). Thus one may expect that many of the salient physical properties of NSM s, which distinguish them from the polycrystalline solid, may essentially be related to the amorphous character of the intercrystalline boundary region. In particular, we argue that the excess specific heat of NSM is due to the extra degrees of s freedom of the atoms in the boundary region. Rather than moving in the usual harmonic local potential, a number of these atoms may experience a bistable potential due to the softening of the local atomic configuration. Such soft potentials are well known to occur in structural glasses (3), w h ere they give rise to a linear specific heat at low temperatures. It should be noted that early experiments on nanostructured Pd (1) have indeed indicated a similar linear behavior of the excess specific heat in a broad temperature range. In this paper we present a simple theoretical model based on some common features of disordered solids. We will describe the extra degrees of freedom due to the local soft potentials in terms of a set of two level systems (TLS s) corresponding to the two equilibrium positions of each atom. A TLS is characterized by a random bias energy AE and is assumed to be coupled to the neighboring TLS through a random interaction s potential due to internal strains and the exchange of phonons. The existence of pairwise mteractions between TLS has recently been suggested for the case of structural s glasses

756

R hi

AND

A Hou

(4,5). Using the pseudospin formalism we can establish the link with the theories of spin (6) and dipolar (7) gl asses and apply the methods developed there to evaluate the average free energy of TLS and from it the excess specific heat. Here we will limit ourselves to s a classical model, neglecting the possibility of quantum tunneling of atoms between the potential minima. Furthermore, we will consider only the replica symmetric solution for the pseudospin glass order parameter Q, which measures the autocorrelations of the local pseudospin polarization. This solution is equivalent to the mean-field approximation for the thermodynamic functions, implying that there is no freezing-type transition into a low-temperature glassy configuration. MODEL AND REPLICA FORMALISM ui = f 1, i = 1,2, . . . . N, where in the i-th soft potential. We the intercrystalline boundary where N << n/. The model

We consider a set of TLS described by the pseudospins s the values fl refer to the two equilibrium atomic positions assume that the sites i are randomly distributed across region of a NSM consisting of ti atomic constitutents, Hamiltonian of interacting TLS is written as s

where h refers to the local energy bias AEi = 2h+ and Jij are the interactions between pairs of TLS s. The free energy 3 of the system must be averaged over all spatial configurations of the TLS s. This so-called quenched average can be performed with the help of the replica method by introducing an ensemble of n identical replicas of the system labeled by the dummy indices CY= 1, . . . . n and using the small-n expansion 2, . . . for the partition function 2 = Tr exp(-/3X). 2 = l+nlnZ+ The random average [Zn],a is performed in two steps. First, we regard hi and Jij as two sets of independent Gaussian random variables with zero mean and nonzero second moments, namely, [hihi],, = 6ijhz and [J$lav = aijJ2, where the parameters h, and J measure the widths of the corresponding probability distributions, and the coefficients oij are related to the interaction range. For example, in the infinite range spin-glass models one sets aij = l/N for all pairs (ij). Here aij = 4(&j) can be considered a function of the distance &j, which falls off rapidly at large &j. In a second step, we then carry out the remaining averaging over the positions of alI TLS without specifying s the actual form of the function 4(&j)Applying the usual transformations from the replica theory we introduce a set of auxiliary fields @ and obtain an expression for the average free energy in the form of a functional integral P3=-~N$J2C~j-~NP2h~-~~~n-1{~D[~~B]expc{~}-1},

j
where the Lagrangian L(q) = L is given by

PI

SPECIFICHEAT OF NANOSTRUCTIJRED MATERIALS

757

In view of the short-range nature of the matrix o;j we cannot derive an exact meanfield theory by evaluating the multiple functional integral by the saddle-point method (6). Formally, the saddle-point value of the Lagrangian &p corresponds to a lowest-order approximation for the free energy, which is equivalent to the mean-field approximation. In principle, one could generate a systematic perturbation expansion around Csp. The saddle point occurs at I$ = < CY:C$ >, where the thermodynamic average is weighted with the last exponential factor in Eq. [3]. The quantity gFP formally plays a role analogous to that of an order parameter in the theories of spin and dipolar glasses (6,7). Here qFP wiIl have a nonzero value at all temperatures due to the presence of random bias energies. RESULTS AND DISCUSSION

We can calculate the relevant thermo$n.mic functions by choosing a replica symmetric value for the order parameter, i.e., qi - qi for all pairs (Y # /3. This leads to a set of coupled equations
qi = (2*)-1 2 J +O ds exp(-z2/2)tanh2

-cm

[(

J2 Caijqj

+ hp

>1
z .

112

PI

At this stage we can consider the remaining position averaging, which will render qi independent of the site index i. It follows from Eq. [4] that this amounts to replacing J2 by an effective parameter J2ag, where a0 z Cj aij. The expression for the internal energy per TLS, i.e., u = N- cY(/~T)/~~ is given in terms of q, namely,
u = +J2(1 - q2) - Ph,2(1 - q) 1

151

from which the excess specific heat 6c, = du/dT is obtained numerically. The result is shown in Fig. 1 for several values of the parameter ratio h,/J. The limiting case without random bias (dotted line) corresponds to a magnetic spin glass and is shown for comparison. In general, 6c, has a broad maximum at T 5 J, its height decreasing with increasing strength of the random bias b. In all cases, 6c, is linear in T in the low temperature limit. A linear low-T excess specific heat is also obtained in the simpler case without random interactions J = 0, which is not explicitly shown here. It should again be stressed that these results have been obtained in the lowest order mean-field approximation for the thermodynamic functions and can thus provide only a qualitative picture of the behavior of the excess specific heat. The problem is that in systems with short-range interactions one cannot apply the usual stability analysis (6) for the replica symmetric solution q(T). Should q become unstable at low temperatures, this would imply a freezing-type transition into a glassy phase with distinct thermodynamic characteristics. The properties of such a phase can be investigated analytically within the framework of replica theory by assuming that the interactions are infinitely ranged, in which case one can explicitly find a solution with broken replica symmetry (8). In particular, it can be shown that in the low temperature phase the excess specific heat

758

R i=Wc AND

A Ho=

Fig. 1. Excess specific heat calculated for several values of the ratio b/J. top to bottom: b/J = 0.1, 0.25, 0.5, 0.75, 1.0. Dotted line: b/J = 0.

Solid lines,

then behaves as 6% oc T with y x 1.8, in contrast to the above linear behavior. At present, there are insufllcient experimental data on the low temperature specific heat of various NSM to allow a critical evaluation of the theoretical predictions and a selection s of the appropriate microscopic model. If a linear excess specific heat is indeed observed in a given temperature interval, its upper limit will provide an estimate for the model parameter J. Clearly, the overall magnitude of 6% will scale with the concentration N/N of TLS which may be of the order of 10%. s, Finally, it should be noted that in metallic NSM the excess specific heat due to s TLS would be competing with the electronic contribution, s which is also linear in T. A rough estimate shows that the electronic contribution would become dominant in the region below 20 K. Thus the contribution of TLS to SC, is expected to be more easily s determined in nonmetallic systems. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. For a recent review see H. Gleiter, Prog. Mater. Sci. 33, 223 (1989). H.-E. Schaefer, R. Wiirschum, R. Birringer, and H. Gleiter, Phys. Rev. B 38, 9545 (1988). W.A. Phillips, J. Low. Temp. Phys. 1, 351 (1972). C.C. Yu and A.J. Leggett, Comments Cond. Matt. Phys. l4, 231 (1988). S.N. Coppersmith, Phys. Rev. Lett. 67, 2315 (1991). K. Binder and A.P. Young, Rev. Mod. Phys. 58, 801 (1986). R. Pirc, B. Tad%, and R. Blinc, Phys. Rev. B 36, 8607 (1987). G. Parisi, Phys. Lett. A 7 203 (1970). 3