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Rep. Prog. Phys. 53 (1990) 85-179. Printed in the U K
Liquid semiconductors
J E Enderbyf and A C Barnes?

Institut Laue-Langevin, BP 156X,38042 Grenoble, France
Abstract
A review of the electronic and structural properties of liquid alloys which show evidence
for semiconducting behavjour and are characterised by short-range order and a well
defined chemical stoichiometry is presented. The notion that such alloy systems can
be classified as narrow definition or broad definition liquid semiconductors is
introduced.
This review was received in February 1989.
t Present address: H H Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 ITL,UK.
0034-4885/90/020085 + 96$14.00 0 1990 IOP Publishing Ltd 85

86 J E Enderby and A C Barnes
Contents
Page
1. Introduction 87
2. The three regimes of conductivity 91
3. Chemical short-range order in liquid alloys 94
3.1. Introduction 96
3.2. The method of isotopic substitution 101
3.3. Hard-sphere liquids 102
3.4. Ionic melts 103
3.5. Covalently bonded solids 108
3.6. Transition metal chalcogenides 108
3.7. Mass transport 109
3.8. Conclusion 110
4. The structure of liquid semiconductors 111
4.2. Elemental liquid semiconductors 111
4.3. Binary liquid semiconductors (narrow definition) 114
4.4. Binary liquid semiconductors (broad definition) 127
4.5. Mass transport 139
5 . The electrical properties of liquid MnTe 140
5.2. Discussion 141
6. The electrical properties of liquid semiconductors 143
6.2. Empirical methods to estimate AE, r and aV 145
6.3. Review of experimental results 148
6.4. The Hall coeacient 172
7. Conclusions 174
Acknowledgments 175
References 175
Liquid semiconductors 87
1. Introduction
Over one hundred years ago Kirchhoff and de la Rive measured the electrical resistance
of several metals at temperatures just above and just below their melting points.
Subsequently, similar experiments on a wide variety of metals were carried out and
many of these used very sophisticated measuring techniques. But the main conclusion
reached by these early workers still stands today, namely that the ability of metals to
conduct electricity is relatively unaffected by the transition from the solid to the liquid
state. The conductivity of liquid silver close to its melting point, for example, although
half that of the solid, is still greater than that for solid lead measured at room
temperature. In some cases, the melting transition actually increases the conductivity;
liquid Ge, Si, Bi and Sb are all respectable metallic conductors, and even liquid Te is
semimetallic. In fact, of the solid elements of the periodic table, which melt at or near
atmospheric pressure, only B, I, P, S, As and Se are non-metallic in the liquid phase.
It is, of course, well known that the wave-like character of the electrons ensures
that they can move quite freely through a perfectly regular crystal lattice. Pure silver
has a negligible electrical resistance at absolute zero, for under these conditions the
positive ions form a well ordered lattice. For temperatures above the absolute zero,
the ions vibrate about their mean positions; this introduces a measure of thermal
disorder which causes the electrons to be scattered and leads to a finite electrical
resistance. As the temperature is increased further, the disorder becomes more marked
and the extra scattering gives rise to greater electrical resistance. Similar considerations
apply to the behaviour of dilute alloys; the presence of a few foreign atoms of gold
in silver, for example, gives rise to impurity scattering which is temperature-independent
and which causes the residual resistance characteristic of impure metals at very low
temperatures, In the 1950s, the experimental results of Kirchhoff and de la Rive seemed
impossible to understand. Ones training in solid-state physics led one to imagine that
the very large jump in disorder which occurs when a metal melts would be accompanied
by a big increase in electron scattering and so render the liquid metal a poor electrical
conductor.
Another problem that continued to worry solid-state physicists, and which is closely
related to the difficulty just referred to, was the apparent success of the nearly free
electron ( NFE) approximation. This approximation attempts to calculate the properties
of the conduction electrons by assuming that they are influenced to only a small degree
by the array of positive ions which form the crystal lattice. At first sight this is a most
inappropriate model, on account of the magnitude of the charge on the ions; in practice
it turned out to be a very useful scheme and can be employed to account for many of
the observed properties of solid metals (see, for example, Harrison 1959). It should
be remembered that, although the most detailed evidence for the NFE picture was
accumulated in the 1950s and 1960s, the beginnings of this approach can be seen in
the Mott and Jones (1936) treatment of diamond and bismuth.
The reasons behind the success of the NFE scheme began to be understood in the
late 1950s, initially through the work of Phillips and Kleinman (1959). They introduced
the idea of a pseudopotential which, by an elegant cancellation theorem involving the
core states of the ion, ensures that the net scattering can be weak even though the real
potential is strong.
The scene was thus set for the brilliant application of diffraction (weak scattering)
theory to the liquid metal problem by J M Ziman (1961). The Ziman formula is now
part of the textbook literature and the mystery of the low electrical resistivity of liquid
metals is, to a large extent, resolved. The formula allows one to calculate both the
conductivity ( U ) and thermopower (S), from a knowledge of the density, the
pseudopotential in momentum space U (k ) and the structure factor S( k ) for the liquid
metal in question. Moreover, the theory gives a convincing explanation of the well
established fact that most divalent liquid metals tend to have a zero or even positive
temperature coefficient of U. The theoretical foundation for the NFE approach was
discussed by Edwards (1962), Heine (1969) and others (for an excellent review see
Faber 1972) and additional confirmation of its validity was provided by the fact that,
for many liquid metals, the Hall coefficient derived from the free electron formula
R =-l/ne (1)
is in excellent agreement with the experiment. In (1) the electron density n is calculated
by assuming that all 2 valence electrons (1 for Na, 5 for Bi etc) can be treated as free.?
In yet another land-mark paper, Faber and Ziman (1965) generalised the pure
liquid metal formula to the alloy case and again the diffraction theory approach
rationalised a seemingly diverse mass of experimental data. Moreover, in one or two
cases where detailed structural information was available, almost exact agreement
between theory and experiment could be achieved. Indeed, the view was often
expressed in the late 1960s and early 1970s that we had a better understanding of
conduction in the liquid phase than in the corresponding solid.
As so often happens in science, the resolution of one mystery gave rise to another.
A hint of a new difficulty was to be found in the early work of Ilschner and Wagner
(1958) who studied the liquid alloy system Mg-Bi over part of its composition range
close to Mg,Bi2. Both liquid Mg and Bi are Ziman liquid metals, and excellent fits
to the observed conductivity, thermopower and Hall coefficient can be achieved if their
valence is assumed to be + 2 and + 5 respectively. Accordingly, the diffraction theory
of Faber and Ziman predicts a relatively smooth variation of U and S with concentration
if, say, Bi is added to Mg. In fact, as the composition approaches Mg,Biz, (T decreases
dramatically (figure l ( a ) ) and, close to stoichiometry, is much less than would be
expected if diffraction theory were applicable. Subsequently, Enderby and Collings
(1970) showed that the temperature coefficient of (T was positive at stoichiometry whilst
the thermopower changed sign (figure l(b)).
The Ilschner-Wagner study was carried out to test earlier suggestions (Hauffe and
Wagner 1940, Vetter and Kubaschewski 1953) that liquid Mg,Biz was predominantly
ionic in character. The valence of bismuth in this model would, of course, be -3, a
value quite different from that suggested by the NFE model for pure liquid Bi. In later
years, an even more dramatic example was afforded by liquid CsAu (Schmutzler er a1
1976). Here the minimum in the electrical conductivity Q which occurs at stoichiometry
is very deep (figure 2) and, in spite of the excellent metallic character of both liquid
Cs and liquid Au, molten CsAu is totally ionic, with Cs carrying a charge of + 1 and
t R is very difficult to measure and it was only in the early 1960s that the first reliable results became
available (Cusack and Kendall 1960, 1961, Tiiche 1960, Takeuchi and Endo 1961, Wilson 1962, Busch and
TiPche 1962, Enderby 1963). It then became common for theoreticians to say that it was hard to see how,
in a liquid metal, R could be anything other than - 1/ ne. Those of us who struggled to make the measurements
would have been more impressed if such a statement had been made before 1960, but there is no hint of it
in the literature.
ool i
1 1 1 1 1 / 1 1 I
12- (b) A
-- 8-
m

/ I
t
I
d 4-
-
,.-.f, I
, , , , , -
Au a charge of - 1. The idea that Au has a valency of -1 and that Bi has a valency
of - 3 is not as strange to chemists as it is to solid-state physicists brought up on band
theory. As we shall see, the chemicalvalency is, in fact, most appropriate for discussing
liquid semiconductors.
The appearance in the West of the review article by Ioffe and Regel (1960) revealed
an extensive body of research carried out in the USSR on liquid alloys of the type
MOA, where M denotes an electropositive element of valence m and A is a chalcogen
(S, Se or Te). Many (but not all) of these alloys were characterised by r values much
lower than could be anticipated if these alloys were metallic. Ioffe-Regel called all
of these alloys liquid semiconductors and, although most of them are, in retrospect,
better described as metallic or semimetallic in character (Enderby and Walsh 1965),
a number do indeed show properties characteristic of conventional semiconductors.
In parallel with liquid studies in the USSR and in the USA, work on solid amorphous
(or glassy) semiconductors was in progress (Kolomiets 1964, Ovshinsky 1968). It
thus became clear that the absence of long-range order did not in itself preclude the
possibility of gaps in the energy spectrum and the interesting physics which follows
from that. Ioffe and Regel (1960) emphasised two important principles which have
guided much of our later thinking. First, they stressed the significance of the short-range
order and, in particular, the need to consider the chemical origin of this order. Secondly,
they recognised that the dimensionless parameter, ZkF, where Z is the electronic mean
1
10 30 50 70 90
AU l~t.%l
Figure 2. The conductivity of liquid Cs-Au alloys at 600 "C (Schmutzler er a1 1976).
free path and kF the Fermi wavevector, must be larger than unity if conventional
transport theory is applicable. If I is comparable with the interatomic spacing, new
and interesting physics will arise, associated with the localisation of electrons.
The subtle interplay between chemical bonding, atomic structure and electronic
properties implied by the two principles enunciated by Ioffe and Regel will form the
major theme for this article. In the next section we outline the characteristic features
of the electrical conductivity for a wide variety of liquids, show how they can be
classified into three broad types and explain the theoretical background to the
classification. In 8 3 we present the principles involved in giving a quantitative descrip-
tion of the structure of liquids and explore in general terms the relationship between
bonding iype, liquid short-range order and the structure of the corresponding solid.
Solid examples of the structure of liquid semiconductors are presented in 4.
The electrical properties of liquid MnTe are described in 0 5 , in preparation for
D 6 which contains a detailed account of the electrical properties of a variety of liquid
semiconductors. The final section contains a summary of the conclusions for which
a coIisensus has emerged and gives our view of what problems remain unresolved.
In order to limit the scope of the article, and to keep it to a reasonable length, we
shall focus principally on liquids with a well defined stoichiometry like Li,Pb, KPb,
CuTe, Ag2Te, T12Te etc. The transition from semiconducting to metallic behaviour as
the composition varies is itself of considerable interest but will be referred to only
when it helps clarify our understanding of stoichiometric compounds. We recognise
that this is a severe limitation on the scope of the article but we invite readers to note
that much of the book written by Cutler (1977) is devoted to the ranges of composition
in which the transition occurs. Similarly, we shall make no reference to a wider class
of liquid semiconductors where short mean free paths are induced by 'dilution', that
is, by increasing the interatomic spacing thereby enhancing the tendency to localisation
through electron correlation effects. Reviews of this type of behaviour, exemplified
by metal-ammonia solutions and liquid metals as the liquid-vapour critical point is
reached, are to be found in Cusack (1987), Hensel (1982) and Mott and Davis (1971).
2. The three regimes of conductivity
In table A1 of the book by Mott and Davis (1971, first edn), values can be found for
the electrical conductivity and its temperature coefficient for some 150 liquids. The
range is enormous, going from 104 000 a-'cm-' for liquid Na to < R-' cm-' for
liquid S. But perhaps the most interesting feature of the table is the fact that there
are no 'natural breaks'. Liquids exist which have more or less any value of U between
these two limits. In this sense the transition from metallic to insulating behaviour is
relatively smooth. However, if one considers du/dT, a different picture emerges: for
100 000 > U > 5000 R-' cm-' practically all liquids (except the divalent metals referred
to above) have a metallic temperature dependence. In the range 5000 to 500 Cl-' cm-',
an increasing number of liquids are characterised by a positive du/dT. For liquids
with conductivity less than 500 Cl-' cm-', d u / d T is nearly always positive, the silver
chalcogenides, AgzSe and Ag,S (but not Ag2Te),representing two important exceptions.
It is clear therefore that, whilst liquid conductors should not be classified too
rigorously, the three regimes often referred to in the literature (Cutler 1977) represent
a useful framework for our discussion. Let us consider liquid alloys of the form M,A1-,
where y is the atomic fraction of M. We will suppose that the elements M and A are
metallic or semimetallic in the pure liquid state but have different electronegativities;
typical conductivity-concentration plots for liquid alloys are shown in figure 3. (It is
M Y A
Figure 3. Schematic representation of the variation of conductivity with concentration for
liquid alloys M,vAl-J. M is the electropositive element of valence m and A is the
electronegative element of valence a.
not always possible to avoid phase separation in the liquid at accessible temperatures
but that complication does not affect the general argument.) Also in figure 3 we indicate
the magnitude of the conductivities which mark the transition from one regime to
another. For U values of 35000 R- cm-, the electronic mean free path is 3 3 A, a
typical value for the interatomic distance in the liquid phase. In this weak scattering
regime the theory of Ziman is applicable; in particular the electrical conductivity is
not sensitive to the detail of the density of states at the Fermi energy, n(E,) (Edwards
1962). The reduction in of M due to the addition of A is entirely a diflraction effect
and will become marked if the pseudopotential of A differs greatly from that of M.
Many liquid alloys stay in this regime across the whole composition range and where
it has proved possible to test the Faber-Ziman theory by experiment (for example, in
liquid Ag-Au and Cu-Sn), the comparison between theory and experiment has proved
satisfactory. These alloy systems, which are essentially metallic in character, fall outside
the scope of this article and, with the exception of chalcogenide alloys where the cation
has an open d shell, will not be discussed further. It should be noted, however, that,
even though U does not depend explicitly on the density of states in the weak scattering
regime, structure in n ( E )will develop as the alloy composition is changed, particularly
if M and A come from different parts of the periodic table and are therefore charac-
terised by different electronegativities.
For conductivities less than 5000 Cl- cm- but greater than, say, 500 R- cm-I, the
observed electrical properties are believed to reflect the electronic density of states
directly through the energy-dependent conductivity u ( E ) . Thus, Mott (1969) and
others have argued that in the so-called Ioffe-Regel regime
U ( E )= A ( T I ( E ) ) (2)
where A is a constant which is weakly dependent on the specific nature of the liquid
alloy. A knowledge of a ( E ) allows U and S to be determined through:
U=-{ a ( E ) -af
dE
dE (3)
where f is the Fermi-Dirac function and EF is the Fermi energy?.

This regime is of particular interest in liquid semiconductor physics because
many alloy systems are characterised by conductivity values in the range -500-
5000 R- cm-, including pure liquid Te. The minimum value of the conductivity, go,
f In the merallic approximation af/aE is replaced by a sharp function centred on E , so that
o = u(,EF) = A ( n (E F ) ) 2
and
sl--2a k2T(dIn;n))
-
3 e EF
However, the high temperature characteristic of most liquid semiconductors in general renders this approxi-
mation of dubious validity and we shall avoid its use in this article. Similarly, the Boltzmann approximation
which replaces f(E)by exp [ - ( E - EF)/k T ] can yield results seriously in error if used in an uncritical way
(see 56.1). We should also note that (3) and (4) apply only to non-interacting electrons, and are often
referred to as the Kubo-Greenwood equations.
which usually occurs at the chemical stoichiometric composition M a A,, arises in this
model from a deep minimum in the density of states curve (figure 4),nowadays referred
to as a pseudogap. The origin of the pseudogap is almost certainly chemical, that is
to say, it reflects a tendency for M to be coordinated to A and vice versa (hetero-
coordination). The effect of an increase in temperature is twofold.
I
E
Figure 4. Schematic representation of the y dependence of the density of states for
semimetallic alloys close to stoichiometry.
First, it broadens the Fermi function so that, even for a temperature-independent

u ( E ) ,the observed conductivity will, through equation (3), show a positive temperature
coefficient. Secondly, the tendency to heterocoordination will be reduced so that the
depth of the pseudogap and the minimum in v ( E ) will be less pronounced. These
two effects either singly or in combination will lead to an increase in the observed
value of cr with temperature. Furthermore, equation (4)predicts that, if EF crosses
the minimum in v ( E ) ,a change in the sign of S is likely. Enderby (1973), Roth (1975)
and Cutler (1977) have all argued that, as the composition of the alloy varies from
MaA, + SA to MOA, -SA, where SA is excess of element A, EFwill move (figure 4)
from left to right, thereby explaining the sign change in S from positive for excess of
the electronegative element to negative for a deficit. An example of an alloy system
which displays this behaviour is afforded by liquid Li-Pb (figure 5). On the other
hand, n(EF)is finite so that a Knight shift is to be expected and is indeed observed.
Other strong experimental evidence in favour of the pseudogap model is the observation
that the Pauli susceptibility (xP)and the Knight shift ( K ) are found to be proportional
to g2,a result to be expected if equation (2) holds.
Thus, at a qualitative and quantitative level, the pseudogap model can explain in
a satisfying manner the observed electronic properties of a variety of alloys whose
conductivity is characterised by a minimum value at stoichiometry in the range
500 CL- cm- to 5000 CL- cm-I. It rationalises the apparent conflict between a semi-
conductor description (positive d a / d T and a p-n transition of the thermopower) and
a metallic description (relatively small Hall coefficients and significant Knight shifts).
It is a matter of taste whether these liquids are referred to as liquid semiconductors,
poor liquid metals or semimetallic liquids, although we prefer the last description.
The broad definition of liquid semiconductors includes pseudogap alloys as is evident
from the papers of the Russian school (Ioffe and Regel 1960, Glazov er a1 1986). The
nurrow definition applies only to those compounds in which EF is located within a
IC
--
m
d o
1
VI
-5
-10
Pb (at.%)
Figure 5. The electrical conductivity and thermoelectric power of liquid Li-Pb alloys:
0 , 800; 0, 850; A,900; A, 950 "C.
'conductivity gap', a concept to be explained later. It should be emphasised that the

broad definition includes the narrow definition as a special case. Later in this article
we shall present evidence to show that the narrow group of alloys defined in the
theoretical sense above are likely to have conductivities significantly less ihan
500 R-' cm-I.
Before explaining the idea of a conductivity gap, we first ask whether equation (2)
still holds if n ( E ) falls to a value substantially less than that predicted by, for example,
the NFE theory. That is, perhaps, the most controversial aspect of the subject. Until
recently, the consensus view, largely based on the seminal work of Anderson (1958):
was that c ( E ) will vanish, even though n ( E ) remains finite (figure 6 ( a ) ) . The energy
below which a()is zero was referred to as the mobility edge and will be denoted
by Ec for electrons. For the case of hole conduction.E, is the energy above which
a ( E ) vanishes.
Originally, Mott proposed that a(E ) was characterised by a minimum value, amin,
which turned out to be = 350 R-' cm-' for liquids (Mott 1982). Thus, the mobility
edge was, in this picture, very sharp (figure 6 ( b ) ) . However, most workers (including
Mott) have abandoned the concept of the minimum metallic conductivity. A second
model (figure 6( c)) is to suppose that for electrons
\- A -/ b
Ev Ec
E-+
Figure 6. Mobility and conductivity close to a substantial dip in n ( E ) . ( a ) Anderson
localisation. u ( E ) is zero for E,< E < E, because p ( E ) is zero even though n ( E ) is finite.
Ev and E, are usually referred to as the mobility edges. ( b ) The original sharp edge model
proposed by Mott. uminwas regarded as essentially universal of order 350n-I cm-'.
( c ) The 'generic' form of U()used in this paper. Ev and E, are referred to as conductivity
edges. The asymmetry factor denoted r in the text is defined by .,/av.
with a similar expression for holes. Cohen et a1 (1985) have argued that, in the absence
of interactions, v = 1 and a is a constant determined by the band width, the interatomic
spacing and a disorder parameter. An early suggestion that Y = 1 is to be found in the
field-theoretic treatment of the Anderson transition by Hikami (1982).
Although the mobility edge picture has been widely used in discussing liquid
semiconductors (Cutler 1977), it is nowadays generally accepted that the effect of finite
electron-phonon interactions is to delocalise electrons below Ec and that, at sufficiently
high temperatures, cr(E) is finite unless n ( E ) is zero (Thomas 1975). Nevertheless,
for liquid semiconductors like MgTe (figure 7) where the total conductivity (ionic and
electronic) is only -9 R-' cm-' at temperatures in excess of 1400 K, the Kubo-
Greenwood equations imply that a ( E ) must essentially vanish at energies close to EF.
We shall avoid the difficult question as to whether the energy at which U ( E ) vanishes
is a mobility edge modified to take into account electron-ion interactions, or a band
edge. Rather, we shall interpret much of the data in terms of a simple generic form
for a ( E ) of the type shown in figure 6(c). The linear dependence of U on E is a
convenient approximation which can be justified as follows: if conduction band tailing
-
is ignored, n ( E ) E"* at the bottom of the band so that equation (2) implies a linear
increase in U ( ) with E. For the mobility edge model, on the other hand, scaling
theories predict that U Cc E' with Y close to unity. Thus, two quite different models
lead to the linear dependence proposed, although the possibility that band tailing may
lead to a value of U greater than unity for Se-Te mixtures has recently been discussed
by Kao and Cutler (1988a,b).
1200 1250 1300 1350

Temperature (OCI
Figure 7. The electrical conductivity of liquid MgTe.
For convenience we shall label the cut-off energies as Ev and Ec but this does not
imply that we favour the mobility edge picture. Instead, we shall refer to them in
terms of conductivity edges. The constants ac and av can at this stage be treated as
free parameters although we shall show how estimates for these quantities can be made
by reference to experiment. Similarly AE = E = - Ev will be referred to as the conduc-
tivity gap. Liquid Tl-Te is an example of an alloy system for which the experimental
data imply the existence of a finite conductivity gap at temperatures close to the liquidus
(figure 8). Conductivity gaps are well established in amorphous solids so that the
fluidity of liquids as distinct from their lack of crystallinity is not important in this
context. However, the absolute value of 4E and its temperature dependence as well
as the form of a ( E ) above Ec will reflect the fluid nature of liquids through the
temperature dependence of S( k) and the presence of electron inelastic scattering (Mott
and Davis 1971, Mott 1987). We finally note that a negative conductivity gap AE s 0
will correspond to liquids whose conductivities are in the range - 5 O O O n - ' cm-* to
500 a-' cm-' (the pseudogap model) whilst AE > 0 will apply to liquids with a s
500 Cl-' cm-', provided EFfalls in the conductivity gap. A list of those liquids discussed
in this article, together with a summary of their electrical properties, is given in table 1.
3. Chemical short-range order in liquid alloys
3.1. Introduction
The connection between chemical order on the one hand and a gap (pseudo or real)
in the electronic density of states on the other, was implicit in the review paper by
Ioffe and Regel (1960) and has been put on a firm mathematical basis by, among
others, Franz and co-workers (see, for example, Franz et al 1980, Holzhey et a1 1982,
van der Lugt and Geertsma 1987). In order to clarify the nature of the short-range
order for liquid alloys, it is desirable to work at the partial structurefactor (Sap(k)) or
the partial radial distribution function (gap(r ) ) level. The function gap(r ) measures the
probability of finding a @type particle at a distance r from an a-type particle placed
at the origin. In order to understand this in a quantitative fashion, let us consider an
a-type particle at the origin and ask what is the average number of P-type particles
I I I I I I I 1
0 20 40 60 80
0 20 40 60 80 100
T1 lat.%l
Figure 8. ( a ) The electrical conductivity of liquid TI-Te alloys at 800 K: e, Enderby and
Simmons (1969); 0,Cutler and Mallon (1966); W, Cutler and Field (1968). ( b ) The
thermoelectric power of liquid TI-Te alloys at 800K and 1OOOK (Cutler 1977). The
peak-to-peakthermopower used for estimating the conductivity gap is denoted by 4s.
which occupy a spherical shell of radius r and thickness d r at the same instant of
time. That number is given by
dnap= 4 r p P g a p( r ) r2 d r (5)
where pp = N o / V and Np is the number of p species contained in the sample of
volume V .
In figure 9 we sketch a hypothetical gMA(r) for a liquid alloy of the form M,A,.
Let us focus attention on the parameters indicated on the sketch. The chance of finding
M and A separated by a distance less than r, is negligible. Thus, r, measures the
Table 1. The liquids discussed in this article. M = metallic, B = liquid semiconductor

(broadly defined) and N =liquid semiconductor (narrowly defined).
Liquid Classification* Temp. ( K ) U (a- cm-I) duldT
Si M 1713 16 670 -
Ge M 1232 17 670 -
InSb M 810 10 000 -
LiAu M 920 9 200 -
NiTe M 1300 5 500 -
ZnSb B 835 5 280 +
NiSe M 1300 5 200 -
NiS M 1073 5 070 -
CdSb B 748 5 040 +
Bi,Te, B 858 3 360 +
Li,Pb B 1000 2 280 +
Na,Pb B 673 2 160 +
CuTe B 888 2 100 +
Sb2Te3 B 898 1840 +
SnTe B 1093 1800 +
Te B 724 1760 +
PbTe B 1200 1520 +
CuSe B 813 1 240 +
KPb B 848 1022 +
Cu2Te B/ N 1130 700 +
RbPb B/ N 874 455 +
PbSe B/ N 1400 450 +
&,Se B/ N 1273 400 -
Ag2S B/ N 1273 280 -
Ga,Te, B/ N 1223 250 +
Ag2Te BI N 1273 230 +
Cu,Se N 1130 160 +
CsPb B/ N 893 140 +
CdTe N 1350 100 +
In,Te, N 973 100 +
ZnTe N 1573 70 +
T1,Te N 710 70 +
Mg3Bi2 N 1173 45 +
As,Te, N 690 40 +
cu,s N 1130 40 +
MnTe N 1500 25 +
MgTe N 1500 9 +
Sb,Se, N 1000 8 +
T1,Se N 973 5 +
T12S N 600 3 +
CsAu N 873 3 +
As,Se, N 770 10-2 +
Se N 500 -lo-* +
closest distance of approach of M and A in the liquid. On the other hand, the value
of TMMA allows us to define the most probable separation and rd tells us the spatial
extent of the short-ranged M-A interactions. It follows from the definition of g a p ( r )
given in equation ( 5 ) that the value of the integral
r IAI
Figure 9. Hypothetical radial distribution function gMA.
is the running coordination number, i.e. the average number of A atoms within a
spherical shell of radius r, for an M atom chosen to be at the origin. If r, is chosen
as rd, this value of the running coordination number is usually referred to as the
coordination number, which we will write in a generalised notation as fiMA. Similar
definitions will apply to the two other partial radial distribution functions &A( r ) and
gMM(r). It is sometimes Useful to define a close coordination number ?7hA.This is best
achieved (Waseda 1981) by symmetrising the first peak in r g ( r ) about ? M A and
computing fiLAthrough
? 7 L A= 4rh jo 2ir.4,
r(rgh4A(r))symdr.
A further property that should be considered is the ratio of the height of the first
minimum ( h ' ) to that of the first maximum ( h ) . If ( h ' l h ) is 60.1, atoms of type A
coordinated to the central atom M are in SZOW exchange with the bulk (Enderby er a1
1987). A small value of (h'/ h ) implies that the lifetime t, of the coordination complex
formed between M and A is at least i f i 2 D M .Here ( ~ 3 ~ ) is' ' ~a characteristic length
(- ?AA) and DM(= DA in the slow-exchange limit) is the self-diffusion constant of the
M species. The fast-exchange limit occurs when the binding time of the complex is
less than t,, which in structural terms leads to significant values of h ' / h (i.e. finite
- -
values of &,A( r ) in the region of id).For most liquids, D, is io-' cm2 s-l, 2 10 A'
so that t,- lo-" s.
In order to determine g L I p ( rexperimentally,
) we must link this quantity with the
results of diffraction theory. If neutrons or x-rays are incident on a liquid containing
several chemical species, a measure of the amplitude of the scattered waves is given by
where b, is the mean neutron coherent scattering length in neutron scattering (or the
x-ray form factor in x-ray scattering, usually written f , ( k ) ) , and r i ( a ) denotes the
position of the ith nucleus of the a-type. In equation (6) the second sum looks after
the phase relationships of the waves scattered from the nuclei at different positions.
The sum over the a values, on the other hand, takes account of the different scattering
lengths for the different kinds of nuclei or atoms. The intensity of coherently scattered
radiation is given by
and can in principle be obtained from an experimental set-up such as that shown in
figure lO(a). The quantity k is the scattering vector whose modulus, k, for elastic
scattering (i.e. lkol = lk,l) (see figure lO(b)) is given by
k = 2k0 sin 0
Monitor
n
Neutron
source
Sample
1b ) Wavenum ber k, ( o1
lJ Neutron
detector
ko= 2 ~ t l X ,
Figure LO. ( a ) Conventional arrangement for neutron diffraction studies; ( b )the scattering
triangle for elastic scattering /$I = lk,l.
or, since k o = 2 r / A o , k = (477- sin @ / A o ) where ho is the incident wavelength and 0 is

half the scattering angle. To do diffraction experiments an intense source of neutrons
or x-rays is required. For neutrons this is normally a high-flux nuclear reactor, although
pulsed sources based on nuclear spallation will play a major role in the future. X-rays
can be derived from conventional laboratory sources or, if very high fluxes or tunability
are required, synchrotron radiation.
Elementary manipulation of equation ( 7 ) yields an expression of the form
where c, is the atomic fraction of the a species, N is the total number of nuclei and
F ( k ) is a weighted average of the partial structure factors, S,,(k), whose Fourier
transform yields g a p ( r ) . Explicitly
and
where p is the total number density.

Four important points must now be made. First, the neutron scattering length is
isotropic, i.e. it does not depend on k. It varies with isotope and with atomic number
in an irregular manner. Examples of scattering lengths relevant to the study of liquid
semiconductors are shown in table 2. Secondly, the Fourier transform of F( k)
G ( r )=T
'I
2.rr p r
F(k)ksin(kr) dk
Table 2. Examples of coherent scattering lengths (fm) ( 1 fm = IO-%).

~~
Element or Element or Element or

isotope b isotope b isotope b
Ti 1.87 63cu 6.7 Te 5.80

7 ~ i -2.2 65cu 11.1 Iz3Te -0.05
Mg 5.2 Zn 5.69 '"Sb 5.71
25Mg 3.6 "Zn 5.5 123Sb 5.38
32s 2.80 68Zn 6.7 n 8.79
203n
34s 3.48 Ge 10.0 6.99
K 3.67 73Ge 5.02 205TI 9.54
4LK 2.58 Se 7.97 "'Pb 8.80
Ni 10.3 76Se 12.20 208Pb 9.65
"Ni 14.4 Io7Ag 7.64
6 2 ~ i
-8.7 lo9Ag 4.19
69Ga 6.40 li31n 5.39
7'Ga 1.88 ii5~n 4.00
can, for the neutron case, be written as a linear combination of all the radial distribution
functions, i.e.
G ( r ) is usually referred to as the total radial distribution function. Thirdly, the x-ray
form factors b, (k)are k-dependent and b, ( k = 0) increases with atomic number in a
linear way. Thus, the total x-ray radial distribution function is not a linear combination
of g,@(r) since k-dependent form factors remain inside the integral of equation (10)
and lead to a 'convolution broadening' of some of the structural features. Finally, the
above analysis assumes that the scattering is entirely elastic. In practice, there is no
elastic scattering from liquids, and corrections must be applied to equation ( 7 ) to allow
for this.
3.2. The method of isotopic substitution
For a liquid alioy of the form MOA,, equation (8) can be written as
To separate out SA*, SAM and S M M from F ( k ) , bA, bM or both must be changed in a
systematic fashion. The method we favour-the technique of neutron diffraction with
isotopic substitution-has been applied to several systems and exploits the variation
of the neutron scattering amplitude with isotopic composition (table 2). As synchrotron
sources and the associated instrumentation are further developed, the possibility of
changing bA or bM by anomalous scattering (Waseda 1984) will doubtless be realised;
EXAFS will also play a role, but so far most structural studies of liquid semiconductors
and related liquids have used conventional diffraction techniques. The numerical
methods used to extract S,,(k) from F ( k ) have been discussed by Edwards et a1
(1975) and, more recently, by McGreevy and Mitchell (1982) and need not detain us
here.
We now consider the characteristic form of Sap(k)and g,, ( r ) for four cases: the
hard sphere fluid (a good approximation for metals), ionic melts, predominantly
covalent melts, and Iiquid transition metal chalcogenides.
3.3. Hard-sphere liquids

The structure of hard-sphere fluids is governed solely by packing considerations, the
relevant length scale being the hard sphere diameter. Thus, binary sphere mixtures
are examples of weakly coupled systems in which any tendency to heterocoordination
is driven only by statistical geometry. The three parameters which characterise such
, atomic concentration c, (= 1 - c2)
a system are the sphere diameter ratio 6 = u 2 / u 1the
and the packing fraction
In figure 11 we show the theoretical structure factors derived by Enderby and North
(1968) for a model of the equiatomic alloy NaK for which u1= 3.28 A, u2= 4.06 A,
--c - -1 and y = 0.451. These structure factors were shown to reproduce accurately
the total diffraction pattern of liquid NaK. It should be noted that a characteristic
feature of the hard sphere system is that kP2 < k:2 < ky, where k& denotes the position
of the first peak in S,,(k). This result is predicted by the semi-empirical relationships
due to Blitry (1978) which state that
-
ko1 2 -L[7.64-4.32( 220 c0fla - I ) ] .
+ fl2
(J, (+1+ U2
The close coordination numbers begin to depart from a linear concentration dependence
when 6 > 1.15. For example, BlCtry (1978) has shown that for y = 0.535 and 6 = 1.25,
-
the maximum deviation from linearity is 15%, and this occurs at c1 = c2 = 0.5.
Nevertheless, the random packing of hard spheres represents a most useful approxima-
tion for describing the structure of many liquid (metallic) alloys.
When, however, the constituents are from different parts of the periodic table, the
structural effects due to size mismatch must be supplemented by those due to interatomic
forces. This was already clear from the early experimental work on liquid Cu6Sn5
(Enderby et al 1966) in which k& was approximately kins,, in disagreement with
the hard-sphere result. In some cases the wavelength of the Friedel oscillations in the
Liquid sem icon d U ctors 103
0 2 L
k (A-')
Figure 11. The partial structure factors for a hard-sphere equiatomic binary alloy (Enderby
and North 1968). U,:3.28 A; U,:4.06 8, Packing fraction: 0.451.
interatomic potentials becomes a relevant length scale in determining the overall

structure. One example is afforded by liquid A1-Ge alloys, which have been studied
in detail by Kahl and Hufner (1988). In other cases, heterocoordination is driven by
strong chemical coupling between the unlike species and we now consider a class of
fluid where this feature is most obvious-ionic melts.
3.4. Ionic melts

In contrast to hard-sphere systems, ionic melts are examples of strongly coupled systems
where both the short-ranged and the long-ranged structures reflect the importance of
chemical bonding, which can, at least to first order, be expressed in terms of pair
potentials & ( r,) whose general form (Huggins and Mayer 1933) for rigid ions can
be written as
with a,p =+,-.

The choice of the parameters appearing in equation (13) differentiates one potential
from another. For example, Fumi and Tosi (1964) allow 2, and Z - to take the full
ionic values (i.e. f 1 for alkali halides) and use the Mayer (1933) values of the
coefficients Cap and DaP. The ways in which B,, and a,, are determined are too
complicated to discuss here but have been carefully summarised by Sangster and Dixon
(1976).
When the theoretical k-space or r-space structures corresponding to interionic
potentials of this form are compared with experiment, remarkably good agreement is
obtained so far as the alkali halides are compared (Rovere and Tosi 1986). For example,
for molten NaCI, theory suggests that g+-( r ) , g++( r ) and g--( r ) exhibit the important
property of charge cancellation for r b 5 A. This effect, first emphasised by Woodcock

and Singer (1971), leads to a definite phase relationship between the three pair
correlation functions. In k-space, heterocoordination (driven in ionic systems by charge
cancellation) is signalled by a negative-going peak in S+-( k ) at the same value of k
for which S + + ( k ) and S - - ( k ) have their maxima. This is in sharp contrast to the
situation for hard-sphere mixtures (figure 11). The predicted structure shows the
unexpected but significant property of first coordination sphere penetration by species
of the same charge. Finally, g++( r ) and g--( r ) turn out to be very nearly the same in
spite of the big difference in anionic and cationic size. All of these predictions are
confirmed by experiment, as can be seen from figures 12 and 13 (Biggin and Enderby
1982).
Figure 12. The partial structure factors for liquid NaCl at 1148 K (Biggin and Enderby 1982).
Theories of the halides of divalent metals are less well developed than those for
alkali-halide systems but they have already exposed several important features in both
Sap(k ) and gap ( r ) . Theory predicts, for example, that first-shell penetration will be
significant for large cations like Ba2+and that charge cancellation will occur for r b 6 A.
The fact that 2, = 2 2 - means that g++(r ) and g--( r ) are different so that the charge
cancellation is not obvious in the partial radial distribution function. In k-space,
glrl
Figure 13. The radial distribution functions for liquid NaCl at 1148 K (Biggin and Enderby
1982).
however, the strong dip in S+-(k)is again clear evidence for heterocoordination. The
experimental data for BaCl, are shown in figures 14 and 15.
As a general rule, simple force laws like that given by equation (10) are satisfactory
for the larger cations like Ba" and Sr2+but less so for the smaller ones. In their work
on molten ZnCl,, for example, Biggin and Enderby (1981) found no penetration of
Zn2+ into the first coordination shell (figure 16). The relatively close-packed nature
I-
5
Y
OK
1
, I I I I I I
0 2 4 6
k (A)
Figure 14. The partial structure factors for liquid BaCI, at 1298 K (Edwards et nl 1978).
g(r)
1 I //, ...I I 1 1 1 I
r [AI
Figure 15. The radial distribution functions for molten BaCI, at 1298 K. Full curve, gB&](r ) ;
broken curve, g,,,,( r ) ; dotted curve, g B a B a ( r ) .
L
r (A,
Figure 16. The radial distribution functions for molten ZnCI, at 600 K. Full curve, gZncl;
dotted curve, gznzn(r); broken curve, gC,=,(r). For clarity gznz,(r) has been displaced by
+0.2.
of C1- in the melt, together with the small size of Zn2+,gives the essential clue to the
structural properties of this liquid. The C1- structure provides tetrahedral sites for the
-
Zn2+ to occupy ( Fc,C,/JZnCl= 1.62 f0.4 J(8/3))so that penetration of like ions into
the first coordination shell cannot occur. Thus, the existence of the stable complex
(ZnC1J2- is confirmed by diffraction data and this situation is quite different for barium
chloride and strontium chloride, where penetration effects play a major role in determin-
ing both structure and dynamical behaviour. Ionic-type interactions are successful in
accounting for the characteristic short-range order of molten ZnCI,.
However, at the level of partial radial distribution functions, departures from a
purely ionic model become clear. For example, the observed value for fznzn(3.8A) is
too short for model potentials based on equation (8) to be applicable. Ferrante er a1
(1987) have addressed this specific problem as well as a more general one concerning
the stability of complexes. A similar situation holds for liquid MgC1, and NiCl,; in
both of these cases, simple ionic interactions are unable to explain the short metal-metal
distances observed experimentally (Biggin et a1 1984, Newport et a1 1985) and must
be modified to take into account what is usually referred to as covalency. By covalency,
we mean those interactions which change the charge distribution of the valence electrons
of atoms relative to some conceptual extreme represented in our case by the ionic
model. Attempts to find quantitative measures of departure from ionicity or relative
ionicity, though having a long history (Chelikowsky and Burdett 1986), are unlikely
to yield numbers of universal applicability (Catlow and Stoneham 1983). Our approach
will be to attempt to model the structure of liquid semiconductors in terms of ionic
interactions and then consider whether departures from the model are significant-a
procedure which is itself, of course, subjective.
In spite of the fact that a proper description of the structure of most molten salts
requires more complicated interaction potentials than those associated with purely
ionic forces, three general principles have emerged from diffraction studies (tables 3
and 4). First, 7+- in molten salts is close to but in general less than that for the
corresponding solid, and is, to an excellent approximation, given by the sum of ionic
Table 3. Near-neighbour distances in molten salts.
-
r+ - r+- Sum of
(observed) (solid) ionic radii?
Melt (A) (A) (A)
MgCI, 2.42 2.53 2.47
ZnCI, 2.27 2.27 2.55
NaCl 2.78 2.81 2.78
CaCI, 2.78 2.78 2.80
SrCI, 2.90 3.03 2.93
KCI 3.06 3.14 3.14
BaCI, 3.10 3.18 3.15
RbCl 3.20 3.27 3.28
NiI, 2.58 2.75 2.89
t Weast (1975).
radii. This fact will be used in deciding whether the ionic model is a valid first
approximation and, if it is, what the oxidation states of the ions are. Secondly, the
number of unlike ions in close contact with the ion at the origin (fit-)is usually less
than the solid-state coordination number and largely reflects the increase in specific
volume at melting according to the semi-empirical formula (Ohno and Furakawa 1981,
Biggin and Enderby 1982):
ti:-
V,
(liquid) = ti (solid) - (v)( 7+(liquid
F+(solid))
Table 4. Coordination numbers.
Cationic Coordination
radius T:-i AS- number
Melt (A) (observed) (equation (14)) in solid
MgCI, 0.66 4.3 4.1 6

ZnC1, 0.74 4.3 3.5 4
NaCl 0.97 3.9 4.0 6
CaCI, 0.99 5.3 5.8 6
SKI, 1.12 5.1 6.5 8
KCI 1.33 4.1 4. I 6
BaCI, 1.34 6.4 7.5 8
RbCl 1.47 3.5 3.8 6
where V, and V, are the molar volumes of solid and liquid respectively. Finally, 7--
and f++ together with fi-- and 3++for the liquid are comparable with the corresponding
quantities in the solid. We conclude that interactions which have a substantial ionic
content in the solid persist across the melting point and give rise to similar short-range
order in both the solid and the liquid phase.
3.5. Covalently bonded solids

The two extremes of metallic and ionic bonding are preserved across the melting point.
For covalently bonded materials, the situation is more complicated. For crystals whose
bonding is predominantly covalent with a network dimensionality of three (see Zallen
1983) and a coordination number of 4,the effect of melting is to destroy the covalent
network so that the liquid becomes metallic. The heterocoordination is not sufficient
to sustain a pseudogap, even close to the melting point. Well known examples of this
type of behaviour include Si, Ge and InSb.
For crystals with a similar or related structure but with partial ionic bonding,
heterocoordination is maintained across the melting point and is always sufficient to
give rise to a pseudogap (ZnSb and CdSb) and may, in fact, produce a conductivity
gap (CdTe and ZnTe). The three types of behaviour are well illustrated by the electrical
conductivity data shown in table 1.
If the network dimensionality is zero (sulphur), one (Se) or two (As2Se3),the local
coordination is maintained in the molten state, so that in the liquid phase these materials
are true semiconductors (or insulators). However, for chain (Te, Sb2Se3) or layered
structures (Bi,Te3) in which the interchain or interlayer distance is too small for the
molecular network to be considered independent, the liquid will tend to be metallic
in character. The striking differences between liquid Se and liquid Te will be discussed
in detail in 4.
3.6. Transition metal chalcogenides

Alloys of the form M,X, where M is a transition metal (including copper) and X is
a chalcogen (Te, Se and S) are metallic conductors if the d bands (usually hybridised
with the pbands) are on the delocalised side of the Mott (or related) transition.
Nevertheless, these materials show heterocoordination so that the bonding is a mixture
of metallic and ionic or covalent. We shall see in 0 4 that for this class of material,
the characteristic bonding and structure is also preserved across the melting point.
3.7. Mass transport

The viscosity 77 and the self-diffusion coefficients D M and DA for liquid alloys are
sensitive to the nature of the interatomic forces and it is useful to consider the magnitude
of these quantities for metallic and ionic melts in the light of the structural data referred
to earlier.
The viscosities for several liquids at temperatures close to the melting point are
shown in table 5. There is a general tendency for ionic systems to have a somewhat
higher viscosity than metallic systems, but the range of values associated with each
type of bonding strongly overlaps. The exceptionally high viscosity of molten ZnClz
and Si02 is a consequence of the underlying network structure.
Table 5. The viscosities of some liquids close to the melting point.
Liquid 7l(cP) Predominant bonding type
Na 0.69 Metallic
Zn 3.17 Metallic
Bi5.6Pb4.4 1.70 Metallic
NaCl 1.31 Ionic
MgC12 2.14 Ionic and covalent corrections
BaCI, 4.02 Ionic
ZnC1, -io3 Ionic and extended covalent corrections
SiO, (2000 K) -io9 Covalent
Self-diffusion coefficients for a selection of liquids are shown in table 6 , again at

temperatures close to the melting point. The coefficients for metals and molten salts
are comparable (except for ZnCI2) and broadly reflect the viscosity values shown in
table 5. The case of ZnC1, is of particular interest for two reasons. First, DZnand DCl
differ by only 10% and have values which are two orders of magnitude smaller than
those for other molten salts. This implies that the chloride ions in the tetrahedral
complex (ZnC1,)'- are in slow exchange and that the complexes themselves undergo
cooperative motion. Secondly, these dynamical effects are clearly reflected in the
structure (figure 16). The fact that gznzn(r)vanishes for 4.5 < r < 5 8, indicates that
the characteristic binding time must be 3 lo-* s. This figure will be useful when we
consider the evidence for extended covalent networks in liquid semiconductors. The
structural stability of molten ZnC1, is probably the origin of the three-peak structure
Table 6. The self-diffusion constants of some liquids close to the melting point.
DM DA
Liquid ( io5 cm2 s-') ( io5 cm2 s-')
Na 4.05 -
In 1.66 -
Zn 2.02 -
NaCl 8.01 6.35
BaCI, 1.84 4.67
SrCI, 2.16 4.20
ZnCI, 0.0144 0.0158
characteristic of Sznzn(k) (figure 17), the first peak reflecting the intermediate range
order. Similar features have been observed in vitreous S O z , GeSe:, and AS& (Moss
and Price 1985), all of which have high viscosities and network structures in the melt.
I
Figure 17. The partial structure factors for liquid ZnC1, at 600 K (Biggin and Enderby 1981).
A final point is to note that for liquid BaClz and SrC12, DClis greater than DBaor
Dsr. In the solid, these compounds are fast ion conductors, the mobile species being
the chloride ion. Thus, the high mobility of C1- in the solid is maintained in the liquid;
moreover, gclcl(r ) is relatively structureless beyond 6 8, (figure 15), illustrating again
that dynamical behaviour is reflected in the radial distribution functions.
3.8. Conclusion
In its original form, the Ioffe-Regel rule stated that a molten semiconductor retains
its semiconducting properties in spite of the destruction of the long-range order if the
liquid phase conserves the short-range order characteristic of the related semiconduct-
ing crystal. The brief survey presented above shows that in most cases the bonding
and structural characteristics of the solid and liquid phase are indeed similar. This
explains why so many liquid alloys can, i f t h e broad definition is used, be classified as
liquid semiconductors.
However, at another level, the Ioffe-Regel rule is really a tautology. The structure
of both the solid and the liquid is governed by the interatomic forces and these
ultimately reflect the electronic structure. Thus, if the electronic structure changes at
the melting point, the structure will follow suit and vice versa. It should also be noted
that for some liquid semiconductors, notably liquid Li,Pb, there are no equivalent
solid-state compounds, but a cluster of compounds of comparable composition (Li7Pb2,
LiZ2Pb5,Li3Pb and Li8Pb3). The importance of the Ioffe-Regel rule is that it provides
a guide to the likely mechanism of conduction in liquids and allows an educated guess
to be made as to the nature of the short-range order in those liquids where diffraction
experiments of sufficient resolution have not yet been carried out.
4. The structure of liquid semiconductors
4.1. Introduction
Over the past ten years an increasing amount of structural information, both at the
total and the partial structure factor level, has become available for liquid semiconduc-
tors. We shall review the results of these investigations in detail and so develop a
quantitative assessment of the Ioffe-Regel rule. In discussing the structural properties
of the liquid, we shall, where possible, take as the reference point the structure of the
corresponding crystal.
4.2. Elemental liquid semiconductors

4.2.1. Liquid Se and Te. The stable polymorph of Se is the trigonal form with a chain
structure as illustrated in figure 18. Each Se atom is in twofold coordination and the
separation of the chains is such that Se can be regarded as a one-dimensional network
Figure 18. A single chain in the trigonal form of Se.

molecular solid. The bond angle is 102" 50' and the near-neighbour distance is 2.374 A
(Krebs 1968).
There have been several structural investigations of liquid Se in recent years (Suzuki
1976, Edeling and Freyland 1981) and a typical structure factor and the corresponding
radial distribution function are shown in figures 19 and 20, respectively. There are
three important points to be made:
(i) the deep minimum in g ( r ) at 2.9 A for liquid Se at its melting point is a direct
structural manifestation of the stability of local molecular conformations;
(ii) the coordination number obtained from g ( r ) is well defined and is, within
experimental error, 2;
(iii) the positions of the first and second peaks in g ( r ) , 2.38 and 3.78 A, correspond
closely to first and second neighbours along the chain shown in figure 18.
It is clear, therefore, that the essential structural features of the solid are preserved
in the liquid state. Further analysis of g ( r ) indicates that its gross features are well
explained in terms of the freely rotating chain model, with viscosity and NMR data
k [,$'I
Figure 19. S ( k ) for liquid Se at 538 K (Suzuki 1976).
,, I I I I I I I
-
2- -
gLr I
1-
-
suggesting that the chains contain lo4 atoms (Glazov et al 1969) at the melting point.
The presence of rings, which involves detailed knowledge of g( r ) in the 5 8, region,
is especially difficult to detect and, in our view, none of the existing data is of the
necessary quality (particularly with regard to statistical accuracy at high k ) to provide
convincing proof that rings exist. In any case, most authors now agree that the
concentration of chains is much greater than that for rings (Lucovsky 1982).
In figure 21 we compare the structure of the crystal and the liquid. For the crystal,
the number of Se atoms as a function of distance from the origin is indicated by vertical
bars. The shaded rectaagles refer to the liquid and show the width of the peaks in
0 1 2 3 4
r [A)
Figure 21. A comparison of the solid (vertical lines) and liquid (hatched rectangles)
structures of liquid Se. n ( r ) is the average number of Se atoms around a central Se atom
as a function of separation. The horizontal shaded rectangles show the r-ranges over which
the radial distribution function is greater than unity. The coordination numbers are given
in brackets.
g ( r ) (see figure caption). Some of the density in g ( r ) for 3.0< r<3.8 8, arises from
interchain distances but the corresponding interactions are essentially non-bonding;
however, as the temperature increases, these interactions become of increasing import-
ance (Edeling and Freyland 1981).
Before we discuss the structure of liquid Te, it is helpful to compare the solid-state
distances and angles for the group VIb elements (table 7). The underlying structure
should be thought of as cubic (figure 22(a)), the form adopted by metallic a-Po, with
a coordination number of 6. A trigonal distortion (figure 22(b)) gives rise to the
characteristic chain-like structure of both Se and Te. However, the fact that the trigonal
distortion is greater in Se than in Te explains the smaller band gap in the latter. It is
Table 7. Interatomic distances and angles for Se, Te and .-Po (Krebs 1968).
First 'Second'
neighbour neighbour
Element (d,) (4) d2/ d, Bond angle
Se 2.37 3.43 1.45 102" 50'

Te 2.88 3.45 1.20 101" 46'
&Po 3.36 3.36 1.00 90"
Figure 22. ( a ) The cubic structure of metallic a-P,. ( b ) The trigonal distortion of ( a )
which leads to helical changes characteristic of solid Se and Te.
clear also that for smalZ distortions, the distinction between bonding interactions within
a chain and non-bonding interactions between chains begins to lose its meaning.
The structure of liquid Te has been determined recently over a wide temperature
range by Menelle et al (1987) with particular reference to the supercooled region. The
results (figure 23) are of interest because they confirm the earlier findings of Hawker
glr I
0 2 4 6 e 10
r (A)
Figure 23. Radial distribution functions for liquid Te at nine temperatures (Menelle er al
1987).
et al (1978) and of Welland et a1 (1985) that the often-quoted work of Tourand and
Breuil (1971) (see also Tourand et al 1972) is seriously in error. Tourand and Breuil
claimed, for example, that at 575 "C,g ( r ) was characterised by three sharp and well
resolved peaks located at 2.97, 3.81 and 4.52 A. The coordination numbers quoted
were 3.0, 3.3 and 7.0. Although the peak positions are close to those of the solid, so
that the Ioffe-Regel rule suggests that liquid Te should retain its semiconducting
properties, the coordination numbers are quite different. Cabane and Friedel (1971)
offered an explanation of the semimetallic character of liquid Te by proposing that
the bonding scheme at high temperatures closely resembled that of rhombohedral As
(figure 24), which is indeed threefold coordinated. At lower temperatures, the structure
was explained in terms of a mixture of threefold and twofold bonding.
Figure 24. The structure of rhombohedral arsenic (Greaves et a1 1979).
It was Cutler (1977) who first pointed out that the electrical properties of liquid
Te and its alloys seem impossible to explain on this model. Three equivalent bonds
on each chalcogen lead to an electronic structure in which EF is located above the
minimum of the pseudogap, i.e. in the conduction band. However, the positive
thermopower of pure Te and its change with alloying, points to EF being beZow the
minimum and located in the valence band.
The Cabane-Friedel model was based on the g( r ) reported by Tourand and Breuil
and obtained from neutron diffraction. Similar results were found in the x-ray studies
of Hoyer et a1 (1975) and Waseda and Tamaki (1975). Hawker et aZ(1978), however,
disputed these results and, as can be seen from table 8, recent neutron diffraction data
from several laboratories are in general agreement with each other and disagree totally
with the earlier measurements. A significant result found by all the workers in the
field is that there is substantial penetration of the first coordination shell by non-bonded
tellurium atoms. This means that it is not possible to identify fiTeTe with the number
of bonds (Enderby and Gay 1980). Even iiZSeTecan be misleading because, as the
results (figure 25) of Welland et al (1985) show, penetration of the first coordination
shell may even occur for r values less than FTTeTe. It turns out, however, that f i f e T e is
2.3 and this, therefore, represents an upper limit for the average number of bonds/atom.
We conclude that nothing in the structural data for liquid Te contradicts the view
expressed by Cutler and Rasolendramitra (1985) that the average number of covalent
bonds per atom is two or even less.
4.2.2. Liquid As. The structure of liquid As has been studied by Bellissent et a1 (1987)
and the radial distribution function is shown in figure 26. The semimetallic nature of
Table 8. The structure of liquid Te by neutron diffraction:
1st 2nd
distance distance Well defined
Temp. (A) (A) ATcTe intermediate
Reference (K) * 0.02 * 0.02 ltO.1 peak?
Hawker et a1 (1978) 773 2.80 4.10 - No

1073 2.80 4.10 - No
Bellissent and Tourand 748 2.84 4.2 -3 No, but weak
(1980) shoulder at 3.7 A
Takeda er al (1984) 733 2.81 4.12 2.6
No
1003 2.91 4.26 3.1
Welland et a1 (1985) 793 2.86 4.14 2.6 No
Menelle er al (1987) 683 2.82 4.11 2.4
773 2.82 4.12 2.9 No
873 2.85 4.06 3.0
~~ ~ ~
i A recent study (x-ray and neutron) of liquid Te by W Hoyer and co-workers (to be published in
WissenschafrlicheZeitschrijt der Technischen Universitut Karl-Man-Sradr) suggests a shoulder at 3.6 A, in
disagreement with the neutron results reported above. However, these workers find that the coordination
number is in the range 2.3-2.6.
g(r I I
1 _ - - - - -
I I
0 1 2 3 4 5
r (AI
Figure 25. The radial distribution function of liquid Te at 793 K in the range 1-5 A. The
dotted line indicates the possibility that non-bonded Te atoms contribute to the first peak
in g ( r ) .
As persists across the melting point, the local coordination being similar in the solid
and liquid state.
4.3. Binary liquid semiconductors [narrow dejnition)

4.3.1. Ag2Te. The structure of liquid AgzTe was investigated at the partial structure
level by Hawker (1974). The isotopic substitution "'Ag + lo9Ag, together with the
r ) to be determined. The results
neutron facilities then available, did not allow gTeTe(
0 2 4 6 8 10
r ti1
Figure 26. The radial distribution function for liquid As at 1090 K (Beliisent et a1 1987).
(figure 27) for gAgAg( r ) and gAgTe( t ) ,though not of an accuracy obtainable with todays
neutron technology, are of interest for three reasons.
(i) The liquid structure cannot be modelled in terms of purely ionic interactions
since both FAAgTe and FAAgAgare shorter than the sum of the ionic radii (table 9).
(ii) The a form of the crystal is a superionic conductor in which the Ag+ ions are
relatively mobile. This is reflected in the liquid phase where gAgAg( r ) is less structured
beyond the first peak than r ) . Such behaviour was mentioned earlier in respect
of molten BaCI, and SrCl,, where the radial distribution function for the chloride ion
(the mobile species in the solid) is comparatively structureless beyond 6 A. Further-
more, the mobility of the silver ions in the CY phase leads to short Ag-Ag distances
(not found in the ideal antifluorite form) and these persist across the melting point
(table 9). Thus, the short-range order characteristic of the high-temperature solid is
maintained in the liquid.
(iii) The presence of appreciable density in &,e( r ) for r = 3.5 %, indicates that the
six or so Te atoms associated with each Ag ion are in fast exchange with bulk Te.
1.8
1. 4
1.0
0 2 4 6 a 10
r [HI
Figure 27. The radial distribution function for liquid Ag,Te at 1273 K (Hawker 1974).
Table 9. The structure of liquid Ag,Te.
Interatomic Observed Calculatedt Solid state$

distance (4 (A) (A)
r ~ g ~ e 2.7 i 0.1 3.37 2.84
rAgAg *
2.8 0.1 3.89 3.28
rTeTe - 5.51 4.65
t Based on the ionic radii quoted in Weast [ 1975) and antifluorite local order (Ag': 1.26 A;
TeZ-: 2.11 A).
$ 'Ideal' antifluorite crystal structure (see, for example, Garba and Jacobs 1986). In the
fast ionic conduction phase Ag+ is the mobile species leading to short Ag-Ag distances
(see table 12).
Although the ionic self-diffusion coefficients have not, so far as we know, been
determined experimentally, the solid state data strongly suggest that DAg will be
considerably greater than DTe, a result consistent with fast exchange.
We conclude that models in which distinct molecules of the form Ag,Te are stable
for times long enough to be structurally significant are not valid. The underlying ionic
model based on Agi and Te2- is a good first approximation, but as is the case for
many silver compounds, requires substantial corrections for covalency.
4.3.2. n2Te and 77,Se. The isotope method (table 2) can, in principle, be applied to
T1,Te and TI,Se, but at the present time the only structural information is at the F(k ) ,
G(r) level. Gay et al (1982) measured the total structure factor F ( k ) for liquid TlzTe
by neutron diffraction with the results shown in figure 28. For this system F ( k ) (in
barns) is given by
F ( k ) = O.351(&,~I(k)- 1)+0.033(&,( k ) - 1) + 0<215(&eT](k)- 1)
which means that, for practical purposes, the contribution from s e T e ( k ) can be
neglected. The total distribution function shown in figure 29 is given by
G(r> O.351(gTIT1 -1 + 0-2l.5(gTeT1(Y)- 1 +O.O33 (gTeTe( r , - )
and like F ( k ) will not be sensitive to gTeTe(r).
Since Te and T1 interact strongly, the position of the first peak corresponds to the
*
interatomic distance fTITe= 3.41 0.02 8,. The peak clearly visible at 4.24* 0.03 8, is
the TI-TI distance yT]T]. In order to find the coordination number, iiTeTI, Gay et a1
decomposed G ( r ) into gTlT](r) and gTeTl(r) by two different methods. In the first
method (figure 29( a ) , Y ) and r2gT]T](
r ) were assumed to be of Gaussian form;
this method yields a value of iiTeT, of 9.6i0.2. Next, r2gTeTi(!-)was assumed to be
symmetrical about YTeTl (figure 29( b)) and this procedure gave a coordination number
of ll.Ok0.2. Several other decompositions were tried but the values for iiTeTI always
fall in the range 9-11. A summary of the structural parameters of liquid TI,Te is given
in table 10. Gay et al concluded that the coordination number is sufficiently different
from 2 to rule out models based on discrete molecules. Consider, on the other hand,
the data in r-space viewed as an assembly of Te2- and TI+ ions. By analogy with the
molten salt work described in 2.3, we expect the following.
(i) The position of the principal peak in gTeTl(r) should be close to the sum of the
empirical ionic radii. This yields a value for fTeT] of 3.58 A, which is in good agreement
with experiment (table 10).
(a1
-n- 0 6 / : , I I , , , , I , I
- 0 2 4 6 8 10 12
-0.3 1
0 0.4 0.8 1.2 1.6

k (A-')
Figure 28. F ( k ) for liquid TI,Te at 873 K (Gay er ai 1982): ( a ) for 0.2 < k < 11 A-'; ( b )
detail for 0.2 < k < 1.7 A. The arrow indicates the position of the shoulder predicted by
the MSA theory for the ionic model.
-l+t
f
i
I
3
I
i
l I
6
1
9
I I l
12
I
i
I
15
f (%I
Figure 29. Full curve: the total radial distribution function for liquid T1,Te. G ( r ) decom-
posed in10 gTeTe(r) and gTlrr(r)by supposing that: ( a ) r2g(r) is of Gaussian form; ( b )
r2g(r ) is symmetrical about FTeTI and FTITl.
Table 10. The structure of liquid Tl,Te.
Interatomic Observed Calculated?

distance (A) (4
lTlTe *
3.41 0.02 3.58
TI TI *
4.24 0.03 4.13
fTITe - 5.84
1.47 A;
? Based on the ionic radii quoted in Weast (1975) and antifluorite local order (TI+:
Te2-: 2.11).
(ii) FT,,,/i&, should correspond to the equivalent quantity for BaCI, since the
ratio of the ionic radii for TlzTl is comparable with that for BaClz. The value found
by Gay et a1 was 0.80 and agrees almost exactly with that found for BaC1,(0.79).
Gay et a1 also considered the consequences of the ionic model in k-space. To do
this, they solved the MSA equation for hard spheres of radii 2.3 and 3.6 8, interacting
through a Coulomb potential. Their results are shown in figure 30. The 'Coulomb'
k) out of phase with the other two; the 'hard-sphere'
peaks are clearly visible with STITe(
1 1 ' 1 I l l I I 1 I 1
0 2 Ir 6 a 10
k 6-')
Figure 30. MSA partial structure factors for liquid TI,Te: full curve, STlTe(k);dotted curve,
STeTe(k); broken CUWe, S ~ i ~ i ( k ) .
peaks are, by contrast, in phase. It will of course be clearly of great interest to measure
STITe( k) and STITI(
k ) , STeTe( k) by the method of isotopic substitution. However, when
the theoretical structure factors are inserted into the relevant expression for F(k), two
predictions about its behaviour can be made:
(i) the existence of a strong peak at 2.3 A-' where the hard-sphere peaks are in
phase; and
(ii) a low-angle shoulder at k = 1.5 A-' where the Coulomb peaks tend to cancel
out (figure 31).
The first feature is clearly visible in figure 28(a) and a careful study of the low-angle
region with two different instruments made by Gay et al (1982) reveals a shoulder in
the region k - 1.5 A-' (figure 2 8 ( b ) ) .
:::VI
0.6
0 2
I I
4
, I
6
I I
e
, j
70
k [A-']
Figure 31. The predicted total structure factor for liquid Ti,Te.
The conclusions of the structural work, albeit at the level of total scattering functions,
are that the underlying ionic structure of liquid T12Te is based on Te'- and T l' ions.
The corrections for covalency effects are small when compared with those required
for Ag2Te. This conclusions is supported by Paulick et a1 (1985) who, on the basis of
nuclear quadrupole resonance studies, claim that the bonding in liquid TlzTe is
considerably more ionic in character than that for Ag,Te. Theoretical studies by
Robertson (1983) have confirmed the ionic character of T12Te.
There has been considerable dispute about whether the compound TI2Te actually
exists in the solid state. The recent work of Guseinov et a2 (1986) appears to confirm
the existence of crystalline T1,Te but this rather brief report does not allow a comparison
between the structural parameters of the liquid and solid to be made.
Structural studies of both T12Teand TI2Sehave been carried out by x-ray techniques,
again at the total structure factor level (see, for example, Matsuda et al 1985). The
convolution effects mentioned in 0 3.1 mean that r-space data have a lower resolution
than those found in the neutron work. Nevertheless, the conclusions derived from the
studies of liquid T1,Te are in good agreement with those of Gay er a1 (1982). Matsuda
et al find that the structure of liquid T1,Se is broadly similar to that for T1,Te; moreover,
the short-range order characteristic of the crystal phase is preserved across the melting
point (table 11).
4.3.3. &Se and Ag,Se. In preparation for a detailed study at the partial structure
level of these two liquids, Barnes and Enderby (1989) have determined F ( k ) for
''Cu2Se and ""'Ag,Se with the results shown in figures 32 and 34. The corresponding
Table 11. Structure of liquid and solid T1,Se.
Liquid 3.40 7.4

Solid 3.35 7.7
Antifluorite structure 3.38i 8
t Based on the ionic radii quoted in Weast (1975). (TI: 1.47 A; Se2-: 1.91 A.)
-0.51 :::
-1.01
0 2.5 5.0 7.5 10.0 12.5 15.0
k [A-',
Figure 32. F ( k) for liquid "Cu,Se at 1420 K.
-2
0 1 2 3 4 5 6 7 8
r [AI
Figure 33. G(r ) for liquid 65Cu,Se at 1420 K.
total radial distribution functions are shown in figures 33 and 35. From the data given
in table 2, it follows that F ( k ) and G(r) (in barns) are given by
F ( k ) =0.54(S,,,u(k)-1)+0.39(S,,,e(k) - l ) + 0 . 0 7 1 ( S ~ e ~ e ( k1)
)-
Cu,Se:
G ( r )=0*54(gcucu(r)- l)+0.39(g,,se(r)-l)+O.O71(gS,se(r) -1)
F ( k ) =0*16(SAgAg(k)- l)+0-21(SAgSe(k)- 1)+0-071(Ssese(k)- 1)
Ag,Se:
G ( r )= O.lb(gAgAg(r)- 1) 0q21(g,4gSe(r)- 1) + o*071(gSeSe(r)- l ) .
The relative weighting of the three structure factors for Cu$e is comparable with
that for T1,Te and, indeed, the total structure factors for liquid Cu,Se and T12Te are
similar. In particular, the charge ordering shoulder is clearly visible at 1.7 A-', as is
the 'hard-sphere' peak at 3.1 A-'. In r-space, on the other hand, there are significant
I I
0.4
0.2-
.,-.. I
-
CI
. *
I
c I I
0 5 10 15
k d-'1
Figure 34. F ( k ) for liquid Ag,Se at 1150 K.
r I , I I
I I I I
0 1 2 3 4 5 6 7 8
r [AI
Figure 35. G ( r ) for liquid Ag,Se at 1150 K.
differences. There is no feature corresponding to a peak in gcucu(r ) at 2.9 A, which -

suggests that Fccucu is close to ~ c C u S e ,a situation similar to that found for liquid Ag2Te.
The ionic model in its elementary form is therefore not applicable to liquid Cu2Se.
The area under the first peak in G(r ) is consistent with ?iCuSe = = 4. Like solid
Ag,Te, the high temperature form of Cu,Se is a superionic conductor with a somewhat
complex structure. It is, however, clear from table 12 that, in general terms, the
short-range order characteristic of the solid persists in the liquid phase.
-
For liquid Ag,Se (a borderline liquid with AE 0), the relative weighting of the
structure factors is different from that of either Cu,Se or TI2Te. In particular, F ( k )
will reflect the influence of SSese(k)and this leads to a clear charge ordering peak at
1.7 A-'. In this regard, F ( k ) for liquid Ag,Se closely resembles that shown in figure
44 for liquid CuSe, where again the weighting of Ssese(k)is particularly marked.
Table 12. The structure of Cu,Se.
Coordination
$7 number
Ideal crystal 2.50 2.88 4

(Se around Cu)
6
(Cu around Cu)
High temperature 2.35-2.50 2.35-2.8s -447-5
a-phase
Ionic modelt 2.87 3.3i
Liquid 2.52 f 0.02 *
2.52 0.04 4+4
t Based on the ionic radii quoted by Weast (1975) and antifluorite local order (Cu+: 0.96 A;
SeZ-: 1.91 A).
The real-space structure of liquid Ag,Se is similar to that for Cu2Se, the area under
the first peak being again consistent with 4+4 coordination. The absence of a structural
feature in G(r ) corresponding to 7AgAg probably means that FAAgAg= FAAgSe for this liquid
also. The value of TAgSe (2.63 A) is considerably less than the sum of the ionic radii
(3.17 A). To summarise: Cu,Te (see P 4.4.1),Cu2Se, Ag2Te and Ag2Se are all charac-
terised by short metal-metal distances, indicating that, in each case, the underlying
ionic model based on Cu+, Ag+, Se2- and Te2- needs to be corrected for covalency.
4.3.4. CsAu and Mg3Bi2. Both Cs and Au are monoisotopic so that structural analysis
at the partial structure factor level is not possible. Nevertheless, the careful work of
Martin et nl (1980a, b) allows important conclusions to be drawn about this liquid
semiconductor. The total structure factor F ( k ) shown in figure 36 is characterised by
a hard-sphere peak at 2.1 k1 and the Coulomb shoulder at 1.3 A-. Both of these
features are consistent with the ionic character of this alloy and have been successfully
reproduced by Evans and Telo da Gama (1980) in a theoretical study in the framework
of the MSA approximation (see also Copestake (1983) for further theoretical work).
The total radial distribution function obtained by Martin et a1 (1980a) shows
evidence for substantial penetration of the first shell by like ions and in such cases the
I I I I I I I I
0 2 L 6 8
k (A-]
Figure 36. Normalised total structure factor for CsAu at 913 K (Martin er nl 1980a, b).
The arrow indicates the position of the shoulder predicted by the MSA theory.
apparent coordination numbers fiCsAu or figsAuobtained directly from integrating G(r )

are likely to be overestimates. Biggin and Enderby (1982), for example, showed that,
in molten BaCl,, the apparent coordination numbers are overestimated by about a
factor of two. Thus, the value quoted by Martin et al for figsAu(- 8) is not inconsistent
with the smaller value of 6.3 obtained from equation (14). A summary of the structural
parameters is given in table 13.
Table 13. The structure of liquid and solid CsAu.
Liquid 3.57 -81

Solid 3.69 8
7 Penetration effects mean that this value is an upper bound.
Although in principle the structure of Mg3Bizcan be probed at the partial structure

factor level (table 2), experimental data are available only for the total patterns (Weber
et al 1979). Nevertheless, they clearly show the 'Coulomb' shoulder and the 'hard-
sphere' peak predicted by the ionic model developed by Copestake et a1 (1980). The
interatomic distances and the coordination numbers reflect the solid-state structure
(table 14); on the other hand, FBiMgis too short if the underlying ionic interaction is
assumed to arise from ions of the form Mg'+ and Bi3-, and this is a case where the
charge transfer is incomplete.
Table 14. The structure of solid and liquid Mg,Bi,.
Liquid 3.00 -6 (average)

Solid 3.21 (average) 7 (anti-La,O, structure)
Ionic model 3.73
t For Mg2+ the ionic radius (0.66 A) is that quoted by Weast (1975). No values are given
for Bi3- so that an estimate was made by scaling the quoted values for Sb3- (2.45 A) by
1.26. This factor corresponds to the ratio of ionic radii quoted for Bi3+ and Sb3'.
4.3.5. CdTe. Liquid CdTe has been investigated by Gaspard er al (1987) at the total
structure factor level. The interatomic distance FcCdfe was found to be 2.83 8, and the
close coordination number in the range 3-4. These values support the conclusion that
the short-range order characteristic of the solid persists across the melting point. The
sum of the ionic radii is 3.08 A, suggesting, in agreement with Chelikowsky and Burdett
(1986), that the bonding is substantially ionic in character.
4.3.6. Ga2Te, and In2Te3. The evidence from a number of experiments (Cutler 1977)
apparently points away from an underlying ionic model based on Ga3+ or In3+, and
Te2-. Investigations carried out at the total structure factor level on liquid In2Te3
suggest a value for filnTe of -3, a near-neighbour distance of 2.85 8, (Hoyer et al
1982) and heterocoordination. The similarity between the solid and liquid is evident
126 .
IE Enderby and A C Barnes
(table 15) but data at the partial structure level are required if real progress towards
understanding the bonding characteristics of these liquids is to be made. In a preliminary
account of the structure of liquid Ga,Te,, Hoyer et al(1984) concluded that it is nearly
isomorphic with liquid In,Te,. A careful neutron study of liquid Ga,Te,-, for 0 < y < 1,
also at the total structure factor level, confirmed the similarity in short-range order
between solid and liquid Ga2Te, (Takeda er a1 1983).
Table 15. The structure of solid and liquid In,Te,.
Liquid 2.95 -3 (average)

Solid 2.67 4.0
Ionic model 2.921 -
t Based on ionic radii quoted by Weast (1975) (In3: 0.81 A; Te: 2.11 A).
4.3.7. As,Se3 and As,Te3. Arsenic triselenide is a liquid semiconductor over a wide
range of temperature and non-stoichiometry, its crystalline form having a layer structure
with each As atom coordinated by three Se atoms. The interaction between the layers
is sufficiently weak for the solid to be described as a two-dimensional network, the
stability of which is maintained by extended covalent bonds.
In the liquid state the total structure factor (figure 37) shows the characteristic
three-peak form (Uemura et a1 1978) which has been noted earlier for molten ZnCl,,
k (%)
Figure 37. Normalised total structure factors for liquid As2Se, at: A, 673 and B, 903 K
(Uemura et a/ 1978).
SiO, and other glass-forming systems. In real space, the radial distribution function
is zero for 2.8 < I < 3.0 %.,indicating well defined coordination and slow exchange
(figure 38). The close coordination number is 2.7 and the As-Se bond length is 2.41 A,
both quantities in good agreement with those characteristic of the solid.
L I I I I I I J
0 2 4 6 8
r [AI
Figure 38. Normalised total radial distribution functions scaled by 4 d p for As,Se, at:
A, 613 and B 903 K.
Liquid As2Te, is more metallic in character than As2Se,, and as will be discussed
in 0 6.4, changes from a narrow definition liquid semiconductor to a semimetal as the
temperature is increased above 690 K. Reflecting this change, the total structure factor
is strongly temperature-dependent around 1 A-', the region of k-space at which
intermediate range order is most evident (Uemura et a1 1979).
4.4. Binary liquid semiconductors (broad definition)

4.4.1. CuzTe. Like liquid Ag2Se, liquid Cu2Te is on the borderline so far as the
broad/narrow definition is concerned (see 6.8). Hawker et al (1974) determined the
structure factors of this melt and the partial radial distribution functions derived from
these data are shown in figure 39. By modern standards these functions are of limited
accuracy but they do show (table 16) that the underlying ionic model based on Cu'
and Te2- needs to be modified to take into account covalency corrections as well as
the screening which must arise from the finite conductivity (see 0 4.4.3 below).
4.4.2. CuTe and CuSe. The structure of the stable form of CuTe is based on a cubic
close-packed anion sublattice in which all the octahedral and half the tetrahedral sites
are empty (Hulliger 1968). The anion and cation sublattices are slightly distorted
(figure 40) but not sufficiently to produce Te pairing. In figure 41 we reproduce the
radial distribution functions for liquid CuTe derived by Nguyen et a1 (1982) and in
figure 42 we compare the solid-state structure with that for the liquid. It is clear from
this comparison that the short-range orders in the liquid and solid states are similar.
It follows that the arguments advanced by Folmer and Jellinek (1980) based on the
stereochemistry and XPS studies of solid CuTe might be expected to apply to liquid
CuTe. In particular, the oxidation state of the elements in the compound should,
3.4-
2.8-
z
c
2.2- c-
-
c -
& -
1.6-
Table 16. The structure of liquid Cu,Te.
Interatomic Observed Calculated?

distance (A) (a
?CuTe *
2.53 0.04 3.07
rcucu *
2.67 0.05 3.54
YT~T~ - 5.01
i Based on the ionic radii quoted by Weast (1975) and antifluorite local order (Cu*:0.96 A;
Te2-: 2.11 A).
according to these workers, be written as Cu'Te- and not, as is often supposed,

Cu2+Te2-.
As pointed out elsewhere (Hawker et a1 1978, Nguyen eta1 1982), the gross structural
features of liquid CuTe are consistent with ionic interactions. However, when the
experimental data are compared in detail with simulation studies (Copestake 1983),
it becomes evident that purely ionic interatomic forces need to be corrected for
covalency if the rather small value of ~ c u c u c(figure
u 41) is to be reproduced. Although
it is not easy to establish from structural data alone whether the underlying ionic model
should be based on Cu2+and Te2- or Cuf and Te-, the data given in table 17 clearly
favour the monovalent form of copper.
The crystal structure of the high temperature form of CuSe is quite different from
that of CuTe. In CuSe, two thirds of the Se form pairs with a characteristic bond
length of 2.25 (figure 43). Folmer and Jellinek (1980) have advanced strong argu-
Figure 40. The structure of solid CuTe: 0 = Cu, 3= Te.
1 I I I I
3- -
\
\
2- '
' I
I
-
' I
glr) ' I
.......
*
1. ..,..
.'*
I'
I I I: I I I I I I
ments in favour of the oxidation states represented by Cu;(Se2)'-Se- so that copper

is again in its monovalent form.
Barnes and Enderby (1988b) were able to separate the total diffraction patterns of
liquid CuSe (figure 44) into partial structure factors to high precision by exploiting
the double substitution += 63Cuand natSe+= '%e. The partial structure factors and
the corresponding radial distribution functions are shown in figures 45 and 46. A
summary of the structural parameters is presented in table 17.
In figure 47 we compare structural data for solid and liquid CuSe and from this
comparison it can be concluded that complex anions, either of the form (Se,)- or
( Se2)'-, exist in the liquid state. The coexistence of complex anions and semimetallic
conductivity has been postulated for other liquids, most notably liquid KPb (van der
Lugt and Geertsma 1987, Saboungi et al 1987) where the anionic species is believed
to be (Pb):-; the experiments report'ed by Barnes and Enderby provide experimental
evidence that metallic conductivity and stable ionic clusters can exist together at
6
5
y//n//7/n
(2 92 0.3)
Cu -Te
-
4- (3.6:O.L)
(bl
n(r) 3 -
2-
1-
Te -Te
Table 17. The structure of liquid CuX ( X = Te, Se).
Valence Observed fcUx Calculated fcUx Observed FXx Calculated f x x

X ofcopper (A) (A)? (A) (AH
Te 2 2.82 rt 0.03 2.83 3.66rt 0.05 4.22
1 2.82 0.03 2.82 3.66k0.05 3.72
Se 2 2.52zt0.03 2.63 *
2.40 0.02 3.82
and
3.80k0.02
1 2.52 k 0.03 2.63 2.40rt0.02 3.34
and
3.80k0.02
-IBased on the values of ionic radii quoted by Weast (1975) (Cu2+:0.72 A; Cu*: 0.96 A; Te2-: 2.11 %.; SeZ-:
1.91 A, and FTe- and Fse- chosen to be 1.86 A and 1.67 8, respectively).
Figure 43. The structure of solid CuSe: 0, Se; 2, Se pairs; 0, Cu.
elevated temperatures in the liquid state. It is also interesting to note that short Cu-Cu
distances appear in the liquid which are absent in the solid; these arise, presumably,
in order that the negative charge on the Se pairs can be effectively screened by the
copper cations.
The experimental data (table 17) clearly rule out the possibility of describing the
underlying ionic interactions in terms of either Cu2+ and Se2- or Cu+ and Se-. Little
is known about the effective ionic radii of (Se,)2- or Se- so that the structural data
do not allow the value of y (2 < y G 1) to be determined in the representation of the
liquid compound as CU:(S~,)'~-~'-S~'~'-. In view of the solid-state data, a value of
y close to 1 seems appropriate although this is not entirely consistent with the second
Se-Se distance of 3.80 8, (table 17); but in any case the mechanism for conductivity
in both the solid and liquid is characterised by holes in the valence band so that CuSe,
like CuTe, can be regarded as a p-type semimetal. The fact that two thirds of the Se
ions are paired in CuSe is, presumably, the explanation of its lower conductivity. It
wiIl be of considerable interest to extend the structural measurements to CuS (for
which suitable isotopes exist) if the technical problems in maintaining an overpressure
of sulphur can be solved, but the evidence suggests that liquid CuS will be metallic
and that the liquid will be characterised by a large fraction of anionic sulphur pairs.
4.4.3. Li,Pb. The structure of liquid Li4Pb and its variation with composition has been
investigated by Ruppersberg and Egger (1975). Although data are available only at
the total structure factor level, the negative scattering length of 'Li (table 2) allows
1 I ' I I I l l -
.., ..
. . A
; '. -
A\,
- ,
i
;* , , '
,
:
.
;
-
. .
1- .: .. : ;
.A
B
...' .., i J
.-,'
-e ..
,' :
.;
.",
,
i
-5 - :
k :
/)
0- -
. . .p:
1- : . c
.:.+. ;. .; : :
! \ ,
t,-,r\-
.. .i
,
. i;
4"
I I L l I 1 1 I
0 4 a 12 16 20
A, natCunatSe;B, 65CunatSe;C, " C U ' ~ S ~ .
21 '.
I 1 1 I I I I I
0 4 a 12 16 i
k [%-'I
Figure 45. The partial structure factors for liquid CuSe at 700 "C. The points represent
the unsmoothed data obtained directly from the F ( k ) s shown in figure 44 and the full
curves are smooth fits.
.. ..
*..' ..
....
-1 ; I I I I I I
4 I I
(bl
VI
..
2 4 6 a
r (A1
Figure 46. The radial distribution functions for liquid CuSe at 700 "C. The points represent
the Fourier transform of the unsmoothed data shown in figure 45. The full curves are the
Fourier transforms of the fitted data.
L Se-Se
r (Ai
Figure 47. A comparison of the solid and liquid state structure of CuSe (see caption to
figure 42).
G ( r ) to be decomposed in a relatively unambiguous way. In particular, Scc(k),the

Bhatia and Thornton (1970) charge-charge structure factor given by
see( k, =i:c C;b ( S L i Li ( k, + SPbPb ( k) - 2 s L i Pb( k) + CLi c p b
is, to an excellent approximation, simply the measured quantity
(c;bF( k)/ b t i ) + CLi CPb *
This approximation is valid because cLibLi= -Cpbbpb (see table 2). The total structure
factor and radial distribution function for the stoichiometric composition are indicative
of heterocoordination and a careful analysis of G ( r ) carried out by Ruppersberg and
Egger showed that PLipb=2.95 8, and fiLiPb=2.5. Copestake et a1 (1983) have further
shown that the observed structure can be well explained in terms of a partial charge
transfer model in which the charge on the lithium and lead is 0.5 e and -2.0 e
respectively. The bare Coulomb interaction was screened to allow for the fact that
Li4Pb is semimetallic in character. Copestake et a1 established by trial and error that
the inverse screening length ( A ) was 1.1 A-' and were able to solve the HNC equation
to yield partial radial distribution functions. In order to make contact with experiment,
these were combined to yield Pcc(r)defined by
Pcc(r) = 4 ~ & c ( r )
where gcc(r) is the Fourier transform of S,,(k). The agreement between theory and
experiment (figure 48) is impressive. The negative going peak at 2.95 8, reflects the
heterocoordination and the tendency for charge ordering at large r is clearly seen. It
-3 L I I I I I I I I I 1
0 4 a 12 16 20
r (%I
Figure 48. The quantity Pcc(r)for liquid Li,Pb calculated for the soft-sphere potentials in
the HNC approximation at T = 1075 K (Copestake et al 1983). The inset shows the
corresponding experimental result (Ruppersberg and Reiter 1982) for this quantity (note
the change in scale on the r axis for r > 8 A).
is also worth noting that theory predicts that the negative Pb ions are excluded from
the first coordination shell which is, however, penetrated by the smaller positive Li
ions. It seems clear that a good working model for Li,Pb is one in which there is
partial charge transfer and screening so that the effective pair potential p n P ( r )at large
separations can be written
cp,p (z,zpe2/
r ) exp( - A r ) .
It will clearly be of interest to analyse the experimental data at the partial structure
factor level to see whether the predictions of the model can be tested in detail.
4.4.4. KPb. The pioneering studies by van der Lugt and his colleagues (see, for
example, van der Lugt and Geertsma 1987) have shown that semimetallic behaviour
occurs in liquid-alkali-group-IV metals and that, in some cases, notably K-Pb, Rb-Pb
and Cs-Pb, the minimum in the conductivity occurs at the equiatomic concentration
rather than the octet composition expected on elementary valence considerations. The
existence of heterocoordination is consistent with the thermodynamic study of liquid
KPb carried out by Saboungi et a1 (1986). For liquid Na-Sn there is very strong
evidence for heterocoordination at both Na,Sn and NaSn (van der Lugt and Geertsma
1987), and indications of similar behaviour in the Na-Pb system (Saboungi et 1985).
The structure of KPb has been investigated by Reijers et a1 (1987) and Saboungi
et a1 (1987). Although the structural data are at the total level, they strongly support
the proposal first made by Geertsma et al (1984) that the liquid contains polyanionic
species of the form (Pb,)4- so that the oxidation states can be written formally as
K;(PbJ4-. They arrived at this model by considering the structure of KPb which had
been investigated earlier by Hewaidy et a1 (1964) and was found to be similar to that
of NaPb (Marsh and Shoemaker 1953). The crucial result is that the unit cells for
both compounds contain eight nearly regular Pb, tetrahedra with the 32 alkali atoms
arranged in shells about the tetrahedra. The structural evidence derived from neutron
scattering points to the persistence of this type of local order into the liquid phase
(see also Alblas et a1 (1983) for a neutron study of liquid NaSn). Saboungi et a1 (1987)
were able satisfactorily to reproduce the observed F(k) for liquid KPb provided that
&Pb, clusters are the dominant species, a conclusion which differs from the original
Geertsma-van der Lugt model (figure 49).
k &I
Figure 49. The normalised total structure factor for liquid KPb at 930 K. Open circles:
experimental results. Full line: theory based on K4Pb4 complexes (Saboungi et a1 1987).
This is clearly a case where analysis at the partial structure factor level would be
invaluable; however, in view of the discovery by Barnes and Enderby (1988b, 1989)
that complex selenium ions in liquid NiSe, NiSe, and CuSe coexist with metallic
conductivity, the possibility of long-lived species of the form postulated by Geertsma
and van der Lugt and by Saboungi et al now seems very likely.
4.4.5. NiTe, NiTe,, NiSe and NiSe,. Liquid NiTe, NiTe,, NiSe and NiSe, were
originally studied as examples of alloys which combine heterocoordination with metal-
lic conductivity. Liquid NiSe is especially interesting because its conductivity is 11
orders of magnitude greater than that for pure liquid Se.
The partial structure factors for liquid NiTe determined by Nguyen et a1 (1982)
possess all the characteristic features associated with heterocoordination (figure 50).
The real-space distribution functions show close metal-metal interactions which cannot
be explained simply in terms of Ni and TeZ- (figure 51 and table 18). Screening
certainly helps to secure better agreement between theory and experiment as the
calculations carried out by Copestake (1983) have shown. The short-range order is
preserved across the melting point and the metallic conductivity arises from the
hybridised d/p band. A discussion of the band structure of NiTe has been given by
Strange and Barnes (1985).
Barnes and Enderby (1989) exploited the negative scattering length of 62Ni (table
2) to produce a zero mixture of Ni, and were able, from a single experiment, to obtain
-1 -
I 1 I I I I I
1 2 3 4 5 6 7
k (a-)
Figure 50. The partial structure factors for liquid NiTe at 1203 K (Nguyen et a1 1982).
Figure 51. The radial distribution functions for liquid NiTe at 1203 K (Nguyen et al 1982).
(-1, gNiTe(r); (---), gNiNi(r); ( ), gTcTe()
Table 18. The structure of NiTe. (N?: 0.69 A; Te-: 2.1 1 A).
Liquid *
2.56 0.03 2.541 0.03 3.5610.04
Ionic model 2.80 4.22 4.22
Solid (NiAs) 2.65 2.69 3.65
(average)
directly SSeSe(k) and gSes,(r ) for liquid NiSe and NiSe, . The contrast between S( k )
for pure liquid Se and Ssese(k)in the alloy is evident (compare figures 19 and 52).
The tendency for Se pairing is clear for NiSez (figure 53) and is detectable in NiSe;
thus NiSe, represents a second example where complex species and metallic conduc-
tivity c m coexist. It should also be noted that liquid NiSe, is close to the liquid
miscibility gap. This gap reilects the fact that on the Se-rich side, the liquid alloy is
insulating and is predominantly chain-like (Enderby and Barnes 1985) with nickel in
fourfold coordination. The absence of a comparable miscibility gap in the Ni-Te
system is a consequence of the fact that liquid Te is semimetallic with little tendency
to form stable pairs. Structural measurements on liquid NiTe, (Nguyen et al 1982)
and the high value for U observed in liquid MnTel show that Te pairing is essentially
absent in these alloys.
Sikl
I I J
0 5 10 15
k (A-]
Figure 52. The partial structure factor Ssese(k)for liquid NiSe, at 1000 K.
0 2 4 6 8
r 1%)
Figure 53. The radial distribution function gscs,(r ) for liquid NiSe, at 1000 K.
4.5. Mass transport
Data for the viscosity of a wide variety of liquid semiconductors have been summarised
by Glazov et al (1969); more recent studies have been made by Chaussemy and
cc-workers (see, for example, Chaussemy et a1 1980, Nakamura and Shimoji 1973).
The composition dependence of 7 for liquid Pb,Se,-, shown in figure 54 is typical
for binary liquid semiconductors (broad and narrow definition); a selection of numeri-
cal values is given in table 19.
It is clear from these data that liquid semiconductors have fluidities comparable
with those characteristic of liquid metals and molten salts. Thus, although as we have
seen, local corrections for covalency are common, there are relatively few cases where
the magnitude of the viscosity implies the existence of extended covalent chains or
networks of lifetime lO-'s.
There are comparatively few published data for the self-diffusion constants D M
and DA,but what there are support the conclusion that most liquid semiconductors
limif
Pb,Sel,
0.7 -
8 I I
Liquid Temp.
semiconductors ( K) Reference
Te 773 1.3 Nakamura and Shimoji (1973)

PbTe 1223 2.0 Glazov et al (1969)
SnTe 1143 2.2 Rosen et a/ (1980)
PbSe 1273 2.5 Chaussemy et a! (1980)
TI,S 790 2.7 Janz and Tompkins (1980)
TI,Te 773 2.9 Nakamura and Shimoji (1973)
Ga,Te, 1080 3.5 Glazov et al (1969)
Se 673 68.2 Laugier et a! (1977)
873 7.1
are in the regime of fast exchange. Thus, an experimental study by Rosen et a1 (1980)
for liquid SnTe showed that Ds,was approximately twice that of DT,and of the same
order of magnitude as that for cations in molten salts. A similar conclusion emerged
from a theoretical study of liquid Mg3Bi2(table 20).
Table 20. The self-diffusion constants of liquid semiconductors.
Liquid Temp. D, DA
semiconductor ( K) (io5 cm2 s-) ( lo5cm2 s-) Reference
Mg3& 1123 10.89 3.75 Gopala Rao and Das (1987)

SnTe 1213 15.0 5.7 Rosen er 01 (1980)
1238 14.6 6.4
1263 14.0 7.0
Li,Pb 1023 18 2.0-2.6 Soltwish et 01 (1982)
1173 27 2.0-2.6
5. The electrical properties of liquid MnTe
5.1. Introduction
In preparation for the detailed review of the electrical properties of a variety of liquid
semiconductors in the solid, we focus attention on one particular alloy, liquid
Mno.5-xTeo,5+,,which has been studied in detail by Barnes et a1 (1987). The aim of
this work was to exploit the unique electronic structure of MnTe in order to find, by
experiment, approximate values for the constants a and v which appear in equation
(15). In addition, the work allows an estimate to be made of how E F - E , changes
with small departures from stoichiometry.
Manganese telluride is, at room temperature, an antiferromagnetic semiconductor
with a NiAs structure. The manganese is present as Mn2+,having donated two electrons
to the anion p bands, thereby creating Te2-. The Mn 3d bands would, in the absence
of p-d overlap, appear as two narrow subbands whose splitting is due to intra-atomic
exchange. In fact, MnTe has energetic p-d overlap, a state of affairs typical for several
ordered and disordered transition-metal-chalcogen systems with the NiAs structure
(see, for example, Strange and Barnes 1985). In this respect, MnTe differs from MnSe
and MnO in that the d bands in these latter compounds lie above the p bands because
of the higher electronegativity of the anions (Wilson 1972, Zaanen et a1 1985). The
non-metallic nature of MnTe arises because the intra-atomic exchange interaction
remains sufficiently strong to keep the unoccupied spin states above the top of the
p bands. Another way of expressing this is to say that MnTe is a small gap Mott-
Hubbard insulator (Wilson 1972, Brandow 1977) on account of the high spin dSform
of Mn2+. The non-metallic character survives both the Niel and the melting transition
(Laundy et al 1983). The upper Hubbard states form a very narrow conduction band
of low mobility while the lower d bands are hybridised with the tellurium p bands to
form a broad valence band with consequent high mobility. A schematic density of
states for MnTe based on the work of Allen et a1 (1977), and confirmed by their optical
measurements, it shown in figure 5 5 ; it is unlikely that its general form will be affected
by the melting transition, because the splitting and the hybridisation of the d band are
essentially non-structural in origin.
d5 (lower) d5 (upper1
nlE1
5p-3d
E"
L i
Figure 55. Schematic density of states for liquid MnTe based on the work of Allen et al
(1977). Ev and E, denote the possible locations of the conductivity edges (Barnes et al
1987).
The band model proposed in figure 55 explains at once the observed p-type character
of both solid and liquid MnTe. (The thermopower of the room-temperature solid is
560 p V K-' (Albers and Haas 1964) and is = 300 p V K-I in the liquid phase.) As
pointed out by Allen et a1 (1977), the holes in MnTe are highly mobile with a
room-temperature mobility of p = 115 cmz V-' s-'. Barnes et a1 (1987) therefore con-
cluded that liquid MnTe is predominantly a unipolar (hole-like) conductor and that
the mobility of the holes will be sufficiently high that they can be treated as quasifree.
Moreover, liquid alloys of this type are readily doped, as the many examples quoted
by Cutler (1977) confirm. Added tellurium will move EFtowards the tellurium p band
and therefore to Ev, so that EF- E , will be a strong function of x. Thus, liquid MnTe
is an ideal system to probe, via the Kubo-Greenwood equations, the nature of a ( E )
for the valence band of one particular chalcogenide and has the decisive advantage
that the complications and ambiguities, which arise if ambipolar conduction is present,
are completely avoided. The results for cr and S are shown in figures 56 and 57,
respectively.
5.2. Discussion
Barnes et a2 (1987) took the generic form for cr(E), i.e.
~T(E)=(YV(EV-) E<,
(15)
=O E>E,
and evaluated cr and S from the Kubo-Greenwood equations for three values of av
(500, 1000 and 1500 a-' cm-' eV-'). The Boltzmann approximation was not used.
They then plotted In U ( & ) versus S(EF) for these three choices (at a fixed temperature
of 1500 K) and in this way the need to know the position EF with respect to Ev is
avoided. The experimental data points (figure 58) fit the theoretical curves within
experimental error if av is chosen as 1000 a-' cm-' eV-'. This value, which represents
an average over an energy range of a few kT below E,, will be considered further in
the next section. Barnes et al suggested that the dependence of SEV= EF-Ev on x
(small x) could be approximated by
SE, = (0.42 - 6 . 6 ~ eV.
)
Y
Figure 56. T h e conductivity of liquid Mn,Te,-, at 1500 K.
I I I I I
0 02 O L
Y
Figure 57. The thermopower of liquid Mn, Te,-, at 1500 K.
In a
100 200 300 LOO 500

5 IpV deg-)
Figure 58. In (r versus S plots at 1500 K for the generic model. crv has been set equal to:
A, 500 R- cm- eV-; B, 1000 R- eV-; and C, 1500 a- cm- eV-. The full circles
are the experimental iesults.
However, this formula was based on the Mott sharp edge model for the conductivity
and subsequent analysis with v ( E )= 1000(Ev- E ) has shown that a better approxima-
tion is
SEV=(O.ll- 7 . 0 ~ )eV. (16)
We finally note that, if we attempt to fit the data with the sharp edge model or with
v chosen as 2, the agreement between theory and experiment is not satisfactory.
6. The electrical properties of liquid semiconductors
6.1. Introduction
An unwarranted use of the Boltzmann approximation forf( E ) in the Kubo-Greenwood
equations, together with the exclusive use of the edge model, has led to incorrect
conclusions about the magnitude and the temperature dependence of S and a as the
position of EF moves from below Ev through the conductivity gap to above Ec. We
therefore begin by obtaining some exact results for these parameters for four cases:
6.1.1. Case (a) Unipolar conductor in the limit SE, = Ec - EF= 0 (electrons) or SEv=
E F - E V = 0 (holes). If the energy-dependent conductivity is of the standard form
(T = LYE the Kubo-Greenwood equations yield
LT = vLY(kT)I, (17)
In equations (17) and (18) II= In 2 and, for Y > 1, I , = [ 1 - 2(1-u)]r(

v ) f (v ) where T(v)
and (( v) are respectively the gamma function and the Riemann zeta function. The
most significant result, which appears to have been somewhat overlooked, is that at a
conductivity edge, S depends (apart from the fundamental constants k and e ) onZy
on the conductivity exponent v, and to that extent is universal. The numerical results
are shown in table 21. Many authors in the past have taken k/e = 86 pV deg- as the
edge value for the thermopower. The error arises from an improper use of the well
known equation for the thermopower
Table 21. The thermoelectric power when E , coincides with a conductivity edge (single
band).
Thermopower
Conductivity exponent v (PV deg-)?
1 *205
1.5 k241
2 *282
t Positive if E, = E,, negative if E, = E,.
which is derived from equation (4) on two assumptions. First, the conductivity is
deemed to be constant over an energy range of a few kT before dropping abruptly to
zero at E. Secondly, the Boltzmann approximation is valid. Thus, even if the first
assumption about the constancy of U in the valence band is correct, which, of course,
contradicts equation (2), the second is clearly wrong once EF+ E.
6.1.2. Case (b) AE=O, SEc=SEV=O. Another case where exact results are possible
is for a zero conductivity gap with EF= Ev = E c . Here, for convenience, we restrict
ourselves to the case of v = 1, although other power laws are readily accommodated.
From the standard combination laws for U and S under ambipolar conditions (Mott
and Davies 1971), we find
U = a,(l+ r)kT In 2 (19)
S= (5) 205 p V deg-
and r, the asymmetry factor, is given by ( a C / a V ) .
6.1.3. Case (c) the large gap case (see also Fritzsche 1971). If AE >> kT, cr and S can
be obtained analytically within the Boltzmann approximation. Numerical tests (see
( d ) below) show that this approximation is valid for those systems for which EFdoes
not come within 2kT of the conductivity edges.
Specifically
a( T )= 2avkT [cosh(E,/kT)-i(l-r) eEFlkr] (21)
where the origin for EF is taken as the centre of the conductivity gap.
For the special case of r = 1 (symmetrical hole and electron conduction)

a(T ) = 2cu,kT cosh( E , / k T ) (23)
[ 2)( g+ 21.
S( T ) = - _ke t anh( 2) -
6.1.4. Case (d) General. It is necessary to integrate numerically the Kubo-Greenwood

equations for cases not covered by cases ( a ) - ( e ) above. We have carried out the
necessary integrations for AE = 0, 0.2, 0.4, 0.5 and 1 eV, with r values in the range 0.2
to 5. A selection of the results at three temperatures (800,1000 and 1500 K) is displayed
in figures 59-62.
6.2. Empirical methods to estimate AE, r and a y

Let AS equal the 'peak-to-peak' thermopower illustrated in figure 8 ( b ) (experiment)
and figure 59 (theory); this quantity reflects the p-n transition as EFmoves across the
-1 0 1 2
E,-& (eV)
Figure 59. The conductivity and thermopower at three temperatures derived from the
Kubo-Greenwood equations. c(E ) was assumed to be of the generic form illustrated in
cm-' eV-' (i.e. r = 1) and A E = 1 eV. For other values
figure 6 ( c ) , with ac = av = 1000 0-' .
of a,-,the conductivity ordinate is scaled by a factor a,/lOOO. (-) 1500 K,(---) 1000 K
(displaced by 200 R-' cm-I), (----) 800 K (displaced by 400 O-' cm-I).
600
400 I
-1 0
E- (eV1
1
-LA-1 0
E&
0
kV1
1.o
Figure 60. As for figure 59 with av = 1000 a- cm-I eV-I, r = 1 and AE = 0.2 eV.
conductivity gap from E,, to Ec. Some tedious algebra shows that for case (c) with
r = 1 (equation (24))
(25)
where p = AE/2kT+2.
In other words, AS depends only on AE. For r # 1 (equation (22)), the algexaic
form of A S is too complicated to reproduce here, but for 0.2 6 r 6 5, AS still depends
essentially on the value of AE, the r value having a negligible effect.
For values of AE which are too small for case ( c ) to apply, the Kubo-Greenwood
equations yield the AS versus P E dependence shown in figure 63. The results again
confirmed the universal relationship between A S and AE for r values in the range
0.2 C r C 5. It follows that, provided the p-n transition occurs over a concentration
range sufficiently small so that the variation of AE with x can be neglected, experimental
data like those illustrated in figure 8 ( b ) allow an excellent estimate to be made of A
and its temperature dependence.
5 400
D
200
+zoo rcm-
-1 0 1 -1 0 1
- E F ieV) &-fF levi
Figure 61. As for figure 59 with aV = 1000 Cl- cm-I eV-, r = 1 and AE = 0 eV.
600 -
400 -
I
7 200-
P
-400-
-1 0
E,-, lev)
-4 -1 0
fv-fF(eV1
Figure 62. As for figure 59 with a, = 1000 12-' cm-I eV-', r = 5 and A E 7 0.2 eV,
The value of r, though not affecting AS, can be estimated by considering the ratio
where sp(in)
ip/& indicates the maximum value of the thermopower on the p(n)
side of the transition. The results obtained from integrating the Kubo-Greenwood
equations are shown in figure 64.
If the thermopower indicates that the contribution to U from holes and electrons
is symmetrical (i.e. r = l), the value of vo (indicated by the arrows in figures 59 and
60) allows an estimate to be made of the average value of CY = cyc = a V . A chart to
allow the appropriate conversion to be made is given in figure 65.
In some cases, the n side of the p-n transition in the thermopower cannot be
observed. This happens because a miscibility gap on the metal-rich side of the
stoichiometric liquid precludes experiments on samples with sufficient excess of the
electropositive element (e.g. Ag,Te). In other cases a second stable compound is
t I I I I I , I , , I
0 0.2 0.G 0.6 0 .a 1.o

A E (eV)
Figure 63. The relationship between AS (see figures 8 ( b ) and 59) and the conductivity gap
AE for three temperatures. The relationship is insensitive to changes in the asymmetry
factor r within the range 0.2 < r < 5 .
0.31 I I I
1 2 3 4
r
Figure 64. The relationship between $/in and the asymmetry factor r at 1500 K for six
values of the conductivity gap: A, 0.5; B, 0.4; C, 0.3; D 0.2; E, 0.1 and F, 0 eV.
formed with added metal (e.g. In,Te, + 4In,+ 31n2Te) which, as we shall see below,
may introduce structure in a(E ) over an energy scale comparable with kT. A useful
estimate of AE can, in certain circumstances, be obtained by doubling the one-sided
maximum value of S (usually s,)
and reading off the appropriate value of AE shown
in figure 63.
6.3. Review of experimental results

6.3.1. Introduction. It should now be clear to the readers that a fundamental theory
of the electrical propenies of liquid semiconductors requires first an understanding of
av,r, AE, the position of EF with respect to Ev and Ec (i.e. 6Ec and SEV),and how
each of these quantities varies with temperature and concentration. This will certainly
involve a knowledge of the structure at least at the partial structure factor level and
probably beyond. There remains the question of the correct form for o ( E ) and its
temperature dependence, and here, electron-phonon interactions might be important.
It follows that explanations of how cr and S vary with temperature and composition
based on parametrising av,r etc can end up as little more than curve fitting. Our
approach will be to use the results described in 66 6.1 and 6.2 as a guide to a possible
taxonomy of liquid semiconductors. In other words, we shall attempt to solve the
inverse problem and deduce from the experimental data the fundamental parameters
a, AE, r and SE and then identify trends in the results.
A (eV1
Figure 65. The relationship between 100~,Jcu and A E for three temperatures.
The 'cleanest' system for the experimental determination of v ( E ) is, as we have

explained, liquid MnTe. The experimental results summarised in 0 5 favour the linear
power law ( v = 1) with an average value of of 1000 a-' cm-' eV-', which is less
than that found by Cutler (1977) for liquid T1,Te following a full and careful analysis
which took into account ambipolar conduction. Our estimates for TlzTe (see 8 6.4)
yield an average value of av of 2800 R-' cm-' eV-' with an r value of = 1, in broad
agreement with the conclusions of Cutler (1977). If this range for a, is representative
of tellurides generally, the conductivity and thermopower at which EF crosses Ev or
Ec are given in table 22. In order to bring out the importance of the asymmetry factor
r, results are included for the extreme case of r = 5 , although there is no experimental
evidence that such large values of r actually occur and in fact r is usually less than 1.
However, it is evident that the often quoted figure of -300 R-' cm-' as a lower limit
for semimetallic behaviour is by no means universal. In liquid MnTe, for example,
the thermopower achieves the 'edge' value of 205 pVdeg-' at the composition
-
Mno,,,Te0.,,, for which the conductivity is 90 a-' cm-'. For conductivities in excess
of this, the liquid is semimetallic. For T12Te, on the other hand, Cutler (1971) has
-
shown that the zero gap condition occurs at = 1000 K, at which point (T 300 R-' cm-I.
This illustrates the general point that, for alloys with small band gaps, (T is increased
and S is reduced from their 'edge' values because of ambipolar effects. A further point
to note is the effect of A E - r synergy, whereby corresponding values of (T and S can,
in the absence of other constraints, be reproduced by a combination of large A E with
large r or small AE with small r. Similarly, there is synergy between A E and a so far
as oo is concerned. We shall return to this point when we discuss the available
experimental data for liquid CdTe, Cu,Te etc.
Table 22. Conductivity and thermopower values when E , coincides with a conductivity
edge (ambipolar case).
Temp. AE U S
(R-'cm-'eV-') r (K) (ev) (a-' cm-') ( p V deg-l)?
1000 1 1000 0 115 0

>OS 57 1205
1500 0 171 0
>os 86 *205
5 1000 0 343 -136
>OS 57 at E, *205
286 at Ec
1500 0 515 -136
>OS 86 at E, 1205
430 at E,
2800 1 1000 0 320 0
>0.5 160 1205
1500 0 482 0
>0.5 241 1205
5 1000 0 962 -136
>OS 160 at E, 1205
801 at Ec
1500 0 1443 -136
>0.5 241 at E, 1205
1203 at E,
t Positive if E,= E", negative if E,= E,.

In summary, we can state that, at temperatures not in excess of 1500K, if U >
500 R-' cm-' and the asymmetry factor is not substantially greater than unity, EF is
unlikely to be in a conductivity gap and the liquid is best described as semimetallic.
The converse is, however, not true. Observed conductivities less than 500 a-' cm-'
do not necessarily imply that EFis in a conductivity gap and that the system is a liquid
semiconductor defined in the narrow sense.
6.3.2. Electronegativity digerence as a guide to semiconducting behaviour. A large

difference between the electronegativity of M (xM)and that of A (xA) will favour
ionicity, heterocoordination and the development of a well defined conductivity gap.
It is, however, clear that there is no general quantitative relationship between A x =
I , Y ~ - x ~ ~ , the absolute magnitude of U,,, or whether a particular value of A x implies
the existence of a finite conductivity gap. The lack of a correlation between U and Ax
arises from chemical effects which, by their nature, cannot be taken fully into account
by a single number. On the other hand, general trends do exist when, for example,
M is fixed and A is varied. We consider three types of binary liquid semiconductors
to illustrate these remarks. It is important, in attempting to establish correlations of
this sort, that the same electronegativity scale is used throughout and we have used
the Pauling values as listed by Huheey (1983).
6.3.2.1. Metal-chalcogen systems. Consider the electrical conductivity values sum-

marised in table 23, which refer to a series of liquid compounds of the form MA or
M,A where M is a divalent or monovalent electropositive element and A is a chalcogen
(0,S , Se and Te). We also include, for completeness, Bi2A3,but here the notion of
m o
- 0
Q I P
" 4d
0 0 0 0 0 0
t
o m v , o o m
v , ~ v , p s n v ,
v, "
Yc
C
.-
90
CI
Bi3+ as a cation is not really valid. The electropositive elements (cations) have been
arranged vertically according to their electronegativities and the chalcogenides horizon-
tally. For a given cation, in which the d shell is closed, a reduction in conductivity
occurs as A goes through the series Te+ Se+ S+ 0. An exception is Ag' at low
temperatures but at high temperatures the general pattern of behaviour is once again
observed and, interestingly, Ag2Se and Ag2S are also exceptions to the dcr/dT 'rule'
referred to in $ 2 . (The value for Bi2S3is taken from rather old work and should be
repeated.) The absolute magnitude of the conductivity for a given cation is roughly
correlated with AX and is invariably less than that of pure liquid Te at the same
temperature.
The situation changes dramatically once the cation has an unfilled dshell. The
presence of Ni2+, CO'+ and Fe2+in liquid Te leads to an increase in conductivity and
at stoichiometry U shows a metallic dependence on temperature. In the case of Cu2+
(apparently d9, in fact d'' but with holes in the valence band), the conductivity of
CuTe is close to that of pure Te, a sharp drop occurring between CuTe and Cu2Te,
i.e. as copper goes towards its monovalent state (d"). Furthermore, the metallic
behaviour persists in the selenides and sulphides in spite of the increase in AX. The
conductivity of liquid NiS is some 15 orders of magnitude bigger than liquid sulphur.
The comparison of Ni2+and Mg2+is also revealing. Although on the Pauling scale
their electronegativities are very different (not the case on other scales, incidentally),
these cations are often treated as isomorphic, having essentially the same ionic radius.
The vastly different electrical properties of NiTe and MgTe reflect the importance of
open d levels in Ni". Originally it was thought that the liquid-state application of the
Mott-Hubbard model provides a satisfying explanation of the metallic/non-metallic
behaviour of those liquid alloys which, in the absence of d-band effects, would be
classed as broadly defined liquid semiconductors. In this picture, liquid NiTe, NiSe
and NiS, for example, are on the delocalised side of the Mott transition and are
therefore metallic, whereas liquid MnTe is on the localised side and is therefore
non-metallic. The unusual concentration dependence of U for liquid Cu-Te alloys
can apparently be understood in terms of the two oxidation states of copper.
However, most workers in the field of transition-metal-chalcogen compounds now
agree that, for most cases, the relevant gap is that associated with the p + d charge
transfer. In other words, the gap which separates the metal/non-metal behaviour is
not that between two d bands split by the Hubbard U but is the energy difference
between the occupied hybridised ligand band and the empty dband. The charge
fluctuations in this model can therefore be written as
d" + d n + d"L+d"+'
where L denotes a hole in the ligand band. This point of view is entirely consistent
with the view, for example, that copper is monovalent in copper chalcogenides. The
moving of a charge from the valence into the conduction band no longer leads to a
d"-' final state but to a d"S. final state; the hybridisation screens out a hole in the
valence band by ligand to metal charge transfer.
6.3.2.2. Metal-metal systems. It is, of course, not surprising that, for d-band com-
pounds, the electronic structure of the cation overrides the general trends associated
with electronegativity differences. The same effect, however, occurs for metal-metal
liquid semiconductors, as can be seen from figure 66. The electronegativity difference
for metallic LiAu is considerably greater than that for Mg3Bi2and Na3Sb, which are
Au
LiLPb
iAu
-t
Lead compounds
CsPb pb
a Mg3Bi,
Na3Sb
lbAu
CsAu
\
0 1 2
Ax
Figure 66. Conductivity of stoichiometric compounds close to their melting points versus
electronegativity difference. The conductivity values were taken from van der Lugt and
Geertsma (1987).
semiconductors. On the other hand, the trend in (+ values for gold alloys as the alkali
component is changed follows Ax. The special characteristic of gold alloys arises from
the relativistic contraction of the s levels. The conductivity gap is situated between
the Au s and the Au p states and this gap depends not only on the electronegativity
of the cations but also on a size factor (van de Lugt and Geertsma 1987). For small
ions like Li, the gap disappears and LiAu becomes metallic, in spite of the large
difference in electronegativity.
6.3.2.3. Arsenic triselenide and related compounds.. The Pauling electronegativity of

arsenic is 2.18. Thus Ax for liquid As2Te3is comparable with that for liquid Bi2Te3,
although the conductivities differ by a factor of lo2. Similarly, Ax for As2Se3(0.37)
is appreciably less than that for PbSe (0.68),although the latter has a much higher
conductivity (450 a-' cm-' as compared with a-lcm-').
Both As and the chalcogens have intermediate electronegativities and the funda-
mental reason for the semiconducting character of As2Te, and As2Se3 is that the
electronic structure of As (4s24p3),Te (5s25p4)and Se (4s24p4)allows a two-dimensional
covalent network to be readily established, such that the '8 - N rule' for the coordination
number is satisfied for both elements. Crucial to the behaviour of chalcogens is the
existence of the lone pair or non-bonding electrons which occupy one of the p-function
orbitals and are spin paired. Bonding is effected by the other two porbitals, each
occupied by one electron. Arsenic, on the other hand, is able to contribute all three
porbitals to the covalent network. It is to be expected that such detailed chemical
effects are missed by considerations based only on electronegativity differences.
We therefore conclude that, although / ~ ~ - , values

y ~ l are a usefui guide to the
occurrence of liquid semiconductors, they must be used with caution whenever the
electronic structures of either A or M are likely to introduce specific chemical effects.
6.3.3. Specific liquid semiconductors (narrow definition).

6.3.3.1. MnTe. This has been discussed in detail already and is included here for
completeness. The electrical properties are consistent with an energy-dependent con-
ductivity of the form cr(E)= 1000(Ev- E ) and r = 0 . The value for the observed
conductivities at which E F= Ev is 80 Cl-' cm-' and this corresponds to the chemical
composition Mno.,,,Teo,5,5(i.e. x = 0.015). Consideration of the theoretical conductivity
shown in figure 61(a) suggests that SEV is a more rapidly varying function with x than
was originaily suggested by Barnes et a1 (1987). We find that SEV is given to an
excellent approximation by
SEv= (0.11 - 7 . 0 ~ ) eV
6.3.3.2. TI,Te, 77,Se and 77,s. These liquids are of interest because they illustrate the
importance of ambipolar effects at stoichiometry. They also have received considerable
experimental attention and, in particular, S has been measured over a sufficiently wide
range of concentration to allow AE to be extracted by the method described in 5 6.2.
Examples of the experimental results are shown in figures 8 ( b ) and 67 and the
conductivity gap parameters deduced from the data are shown in table 24. The tendency
for ionicity to become more pronounced through the series Te + Se + S is reflected by
an increase in AEo. Furthermore, the temperature at which the conductivity gap
vanishes shows an increase in the same sense.
Since ip = infor all three systems, r -- 1 so that an average value of (Y = aV= aC
can be estimated from figure 65. The results are shown in table 25. Within experimental
error a does not depend on temperature; it does, however, vary (by a factor of about
3) from one liquid to another and is therefore not universal.
Finally, the experimentally observed variation of S with x allows an estimate to
be made of the changes of SEVwith added chalcogen. The results, together with the
method of calculation, are given in table 26. For small values of x, d(SEv)/dx is
remarkably constant (within a factor of two) for the three chalcogens, which suggests
that, at small excess concentrations, the chalcogen is fully ionised. At the largest
concentrations of Se and S, the tendency for complex species to be formed (already
seen directly in structural measurements on CuSe and NiSeJ is reflected (figure 67)
in the saturation of the thermopower at a value close to $.
Table 24. The conductivity gap for liquid chalcogenides.
AS A (derived Temp. for

Liquid Temp. (observed) from figure 63) a zero gap
semiconductor (K) (pVdeg-') (eV) A=A,-pT (K)
TI,Te 800 300* 10 *
0.17 0.01 0.77 -7.5 x 10-4T 1030
1000 190* 10 *
0.02 0.01
T1,Se 800 470* 10 0.36 f0.01 0.80-5.5 X 10-4T 1450
1000 *
320 10 0.25 iO.01
n2s 800 6201 10 0.50i0.01 1.03-6.6~ 10-4T 1565
950 *
440 10 *
0.40 0.01
Table 25. a values for liquid chalcogenides.
a
(derived from
Liquid Temp. CO figure 65)
semiconductor (K) (a-' cm-') (a-' cm-' eV-')
TI,Te 800 11015 29001 100
1000 32015 2700k 100
1,Se 800 15*2 1500i200
1000 52*2 14001 100
ll,Si 800 5 11 10001200
950 1311 *
900 I00
t The minimum is very shallow for this system. Moreover, an ionic contribution to the
conductivity may exist, so that this value of ct is an upper bound.
6.3.3.3. Ag2Te, Ag,Se and Ag$. The structural evidence presented in 0 4.3 indicates
that the underlying ionic model based on Ag* and X2- requires significant local
correction for covalency, in contrast to the situation for thallium-based chalcogenides.
This conclusion is supported by the nuclear quadrupole spin relaxation studies of
Brinkmann e? al (1985).
The available thermoelectric power data are not sufficient for a detailed analysis
of the form of o ( E ) for all three chalcogenides. According to Dancy (1965) gP for
-
Ag,Te at 1273 K is 100 p V deg-' so that the 'one-sided' method of estimating A E
from ipyields a AE value of -0.08 eV, which implies (figure 6 5 ) that aV=
300
200
100
Se Iot%l
I
r
m
O O
1
Y
-100 -120
- 200 -200
I I I I I
30 40 50 60
Se (at,%)
Figure 67. The change in thermopower with composition for n,Se close to stoichiometry
(Regel 1970). A, 750; and B, 1000 K.
0 0 0 0
0 0 0 0 0
2Z22Z
iitlsislsi
0 0 0 0 0
0 0 0 0 0
O O O O N
o v a q m
w - -
0 0 0 0 0
orno00
m a m o
c
m
2200 a-' cm-' eV-'. Both of these values are comparable with those found for liquid
1 5T12Te.
If the aVvalues appropriate to T1,Se and T12S are applied to Ag2Se and Ag2S, the
conductivity data imply that, for both alloys, A E -0, which is consistent with the
limited thermopower data available for Ag,S (Ditman and Kulikova 1977). The striking
and unusual observation that d c / d T < O for both Ag2Se and Ag,S (see figure 68)
means that, if CY is independent of temperature, d ( A E ) / a T must be positive. This
behaviour is expected if the partially covalent Ag,Se and Ag2S at the melting point
900 -
700 -
500 -
900 1100 1300

T (K)
Figure 68. The temperature dependence of U for three silver chalcogenides close to their
melting points (Glazov et a1 1986).
become increasingly ionic at elevated temperatures, a not unreasonable possibility in

view of the large values of Ax which characterise these alloys. A careful study by
Nakajima et a1 (1982) on the effect of replacing Tl in T12S by Ag yields data which,
when interpreted by the methods described here, support this conclusion (see 0 6.3.3.4
below). However, there is clearly urgent need for accurate thermopower and structural
measurements at temperatures in excess of 1000C if the nature of the silver chal-
cogenides is to be fully understood.
6.3.3.4 CunTe, CuTI,Se,, Ag?7,Te2, Agl7,Se and Ag17,S2. Liquid CuTlTe has been
studied by Satow et a2 (1988), with the results shown in figure 69. The conductivity
parameters, extracted by the methods outlined in 0 6.2 are listed in table 27. The most
100
TlTe 20 40 60
Cu (molohl
Figure 69. The change in thermopower with composition for liquid CuTlTe close to
stoichiometry (Satow et al 1988). 0 , 700; 0, 800; 0,
900 "C.
significant changes induced by replacing one TI in T12Teby one Cu are, in summary:

(i) U(E ) for the valence band is essentially unchanged;
(ii) the slope of a ( ) for the conduction band is reduced by a factor of - 5 at
-
1000 K and of 3 at 1273 K, thus leading to an appreciable asymmetry factor;
(iii) the value of A,, is reduced by about 10% reflecting the high electronegativity
of Cu+ compared with that of Tl+. On the other hand, the temperature factor is
appreciably less.
Similar effects are found for the selenides when the data due to Uemura et a1 (1983)
are analysed (table 27).
The liquid semiconductor AgT1,Se2 has been studied by Uemura et a1 (1982b).
The conductivity gap (table 27) shows a smaller temperature dependence than that
for TI,Se, which means that Ag2Se could indeed have a negative p as suggested in
6.3.3.3 above. The experiments on liquid AgT13S2by Nakagima et a1 (1982) are even
more striking because they show that AS is almost independent of temperature (table
27), which means that AE increases with temperature. Thus, the experiments on silver
ternary compounds are consistent with the suggestion that p might be negative in pure
liquid Ag2Se and Ag2S.
The conductivity parameters for AgT1,Te2 (Uemura et a1 1982a), AgT13Se2 and
AgT13S2are summarised in table 27. For the sulphide they differ from those of most
other liquid semiconductors in that av shows marked variation with temperature.
Furthermore, av for AgT1,Te2 and AgT13S2are quite different from those of pure Tl2Te
and Tl2S. We have no explanation of these effects.
d m d o
T b - "
6 0 0 0 - -
1 1
0 0 0 0 0 0 0 0 0
2zzzFj8FjgFj
+SISi-HSiiiiiiiH
-
0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0
m , - t = N r - y w a w
" - N -
-
c o \ m m m o w o
".".".t-?"Y
0 0 0 0 0 0 0 0 0
6.3.3.5. CsAu, MgTe, Mg3Bi2, Sb2Se3, CdTe and ZnTe. These represent a group of
liquids where, either because of the basic physics or the lack of experimental data,
the inversion methods described in D 6.2 cannot be applied. For example, solid CsAu
is an ionic compound with an energy gap of 2.6 eV and it is not surprising, therefore,
that the liquid is also a semiconductor/insulator. However, the large contribution
from ionic transport makes our inversion methods suspect until a reliable method has
been developed which allows the electronic part of U and S to be extracted from the
measurements. Littlewood (1981), though not addressing this specific problem, has
shown that the electrical conductivity of CsAu around stoichiometry can be well
understood in terms of electrons localised in Fcentres. If r is taken as unity and CY
assumed to be the standard value of 1000 Cl-' cm-' eV-', we find from figure 65 that
the observed ao,assumed to be totally electronic in origin, yields a conductivity gap
of 0.6 eV, if part of uois ionic in origin, as it almost certainly is, A is greatly increased.
For liquid Mg,Bi, and Sb2Se3,the thermopower is zero at stoichiometry, implying
-
that r is 1. For the first liquid it is clear from figure l ( b ) that AE closes rapidly
with excess Mg or Bi so that the AS-AE method cannot be used. The same appears
to be the case for liquid Sb2Se3with excess Sb (Kazandzhan 1968).
Finally, for MgTe, CdTe and ZnTe, experimental difficulties have so far precluded
measurements of S as a function of excess Te, Mg, Cd or Zn. The only data are those
due to Barnes (1986), who found that at stoichiometry the thermopower of CdTe is
+ 84 p V deg-I. Our estimates for AE and the basis on which they were calculated are
shown in table 28.
Table 28. Estimated values of AE.
U0
Liquid AX (Q-' cm-')
semiconductor (Pauling scale) T (K) (electronic part) A (eV)i
CsAu 1.75 873 c3 20.6

MgTe 0.79 1500 9 0.9
Mg,Bi, 0.71 1173 45 0.3
ZnTe 0.55 1573 70 0.4
Sb,Se, 0.50 1000 8 0.5
CdTe 0.41 1350 100 0.2
i Estimated on the assumption that a, = 1000 a-' cm-' eV-', r = 1 and (except CdTe) that EFis located at
the centre of the conductivity gap. For CdTe, the observed thermoelectric power (+84 p V deg-') and U,
can be made mutually consistent if ,-E, is chosen as 0.06 eV and AE =0.2eV. It should be noted,
however, that the r - A synergy means that mutually consistent S and U,,can be found for other choices
of AE.
6.3.3.6. As2Te3 and As2Se3. It is, in principle, possible to follow continuously the
change in conductivity and thermopower for liquid As,Tel-, as y varies from 0 to 1.
So far, results are available for O s y S 0 . 5 5 (Qberafo 1975) (figures 70 and 71). These
data can be well understood in terms of conduction arising essentially from the valence
band with a ( E )= 1080(Ev- E ) , ambipolar effects playing a negligible role. The results
summarised in table 29 imply that As2Te3is a narrow definition semiconductor only
for T s 690 K. Above this temperature, EF is located below the conductivity edge of
the valence band and is therefore semimetallic in character. The effect of added Te
0 20 40
As [at.%)
Figure 70. The conductivity of As,.Te,-, at five temperatures (Oberafo 1975). A, 600; B,
550; C, 500; D, 450 and E, 425 "C.
is to move EF into the valence band and a Kubo-Greenwood analysis of the experi-
mental data shows that
SEV (at 690 K) = (0 - 0 . 7 ~ )
where, as before, x measures the departure from stoichiometry in terms of the formula
As0,4-xTe0.6+x.The effect of added Te on SEV is an order of magnitude less for As2Te3
AS Iat.% 1
Figure 71. The thermopower of liquid As,.Te,-,. at eight temperatures (Oberafo 1975).
A, 400; B, 425; C, 450; D, 500; E, 550; F, 575; G, 600 and H, 625 "C.
Table 29. The electrical properties of liquid As,Te, (Oberafc 1975).

~
T (K) S ( k V deg-')
909 40 1340 7.21

870 52 920 6.83
833 68 610 6.42
800 90 340 5.83
769 110 190 5.24
741 140 127 4.84
714 167 71 4.26
6901 200 43 3.76
667 250 24 3.18
iE, crcsses Ev at this temperature; the data can be fitted with o ( E ) = 1080(Ev-E).
than it is for MnTe or T12Te. This is a direct consequence of the bonding characteristics
of As2Te, discussed earlier.
Liquid As2Se, is a narrow definition liquid semiconductor and represents one of
the few cases where M and A are in 'slow exchange'. Hurst and Davies (1974) have
investigated As,Sel-y for 0.3 <y < 0.55 and for temperatures in the range 580 K to
760 K (figures 72 and 73). In all cases, EFis in the conductivity gap, which is estimated
-
to be 2 eV. Hurst and Davies attempt to explain their data in terms of the sharp edge
model and with simplified equations for ~r and S which ignore ambipolar effects. Not
Y'O.50 I
-2 -
-4 - $, 0.LS 1
\.I
-!
0.40 1
.,
B
% 0.35 \.
-2 - 0.30 s,
-4 -
I I I
1.3 1.5 1.7
1 / T IlO-'K-']
Figure 72. The conductivity of liquid As,.Se,-,. as a function of inverse temperature (Hurst
and Davies 1974).
r
0.7 - y=0.50
-
1
z
-
>
Y
1.1-
E 0.7-
1.1
-
-
-
-
0.35
e
9
-/- .A
-
- 0.7
Y
0.7 - 0.30 - H
1 1
Table 30. The conductivity parameters for cuprous chalcogenides.?
Cu,Te 540 100 *

0.09 0.03 4200 200* S O
Cu,Se 158 172 *
0.36 0.03 2800*200 0.18* 0.04
cu,s 38 325 0.90* 0.05 2400 200* 0.5010.05
~~~~~ ~ ~~ ~
t In each case the temperature is 1400 K (for references see Barnes and Enderby 1988b).
$ Obtained by the 'one-sided' method.
I Obtained by assuming that a is equal to the corresponding thaflium compound (table 25).
c
2ooo CuTe
\
1500 1 \
\
\
" I 1000
\
\
500 c \
\
I I
0.50 0.55 0.60 0.65

Y
Figure 74. The conductivity at the liquidus temperature for Cu, Se,-,. and Cu)Te,-, The .
arrows indicate the sign (t positive; 1negative) of d u / d T (for references, see Barnes and
Enderby 1988b).
of composition the p-type metallic behaviour characteristic of the cupric chalcogenide

becomes p-type semiconducting behaviour as &-Ev decreases. Indeed, it was Cutler
(1977) who first explicitly emphasised the anomalous behaviour of Cu,Te,-, in this
composition range. The fact that such behaviour is reproduced also in the Cu,Se,-,
system suggests that it has a common origin.
The explanation of this unusual behaviour is, we believe, to be found by recalling
that both CuX and Cu2X (X=Te, Se) show clear structural evidence for hetero-
coordination; this means that a(E ) will be characterised by two minima (a pseudogap
for the cupric compound and a real gap for the cuprous compound) separated in
energy. In order to get a feel for what might happen in practice, consider the two sets
of a(E)shown in figure 7 6 . These are, of course, highly idealised but the resulting
/
t
--
Y
> /
/
p
- Cu2Te
@
.--,-
-7
CuSe
CuTe
I , I ,
0.50 0.55 0.60 0.65
Y
Figure 75. The thermopower at the liquidus temperature for Cu,.Se,-,. and Cu,.Te,-y. The
arrows indicate the sign (T positive; & negative; +zero) of d S / d T (for references, see
Barnes and Enderby 1988b).
I CuTe Cu2Te
-0.4 lev)-
Figure 76. Two simplified models for a(E)applicable to a liquid chalcogenide with
heterocoordination at twc compositions.
behaviour of U and S shown in figure 77 brings out the essential physics. At composi-
tions intermediate between Cu2X and CuX, d a / d T is almost zero for case ( a ) and is
clearly negative for case ( b ) . In other words, the structure in a ( E ) over an energy
range of a few kT can within a rigid band model give rise to negative (metallic)-like
temperature coefficients of conductivity.
In the light of these results for Cu, it is interesting to consider the experimental
data for In,Te,-, due to Popp et a1 (1974). The two-peak structure (figure 78) found
for the thermopower by these workers confirmed a similar result by Ninomiya et a1
(1972) and has recently been reconfirmed by Hoyer and Tschirner (1983).
In order to understand this unusual behaviour, it is necessary first to recall that
the chemical valencies of indium are +1 and + 3 so that heterocoordination in the
-1 0 1 -1 0
Y -200
-600
-1 0 1
(eV1
Figure 77. The conductivity and thermopower derived from the energy-dependent conduc-
tivities shown in figure 76: (-) 1500K and (---) 1000 K.
liquid might be expected at the compositions In2Te and In2Te3. In,Te, does indeed
melt congruently and the structural evidence reported by Hoyer et a1 (1982) points to
heterocoordination. InTe also melts congruently; in the solid (Wells 1984) InTe is
characterised by two non-equivalent In sites, the environments of which suggest that
the oxidation states should be represented by 111+1n~+(Te'-)~.If this formulation
persists in the liquid, InTe is likely to be less ordered than either In2Te3 or In2Te.
Accordingly, we have modelled the In-Te system by the highly idealised ( + ( E )shown
in figure 79 and again assumed rigid band behaviour; as for the Cu-X system, we are
concerned only to establish general trends and not to fit the experimental data in detail.
It is apparent, however, that the a ( )shown reproduces all the gross features of the
measured thermopower. In particular, the presence of a zero gap compound ( In2Te)
-
above a real gap compound (In2Te3)reduces 2, by 50 p V deg-'. Furthermore, the
maxima in the thermopower are observed to occur at compositions containing excess
Te, a result predicted by the theory. Thus, both the location and the modest value of
Spclose to In2Te3are well explained in terms of the model. The model predicts that
d(+/dT should be zero at compositions close to In,Te and this is indeed observed.
We finally consider the interesting a ( y ) and S ( y ) plots for Ga,Te,-,v (Valiant and
Faber 1974, Tschirner et al 1975) shown in figure 80. These data differ from those for
Te 0.9 0.7 0.5 0.3 0.1 In

Y
Figure 78. The observed conductivity and thermopower of liquid In,.Te,_? at 973 K (Popp
er a1 1974).
In2Te3in that no further maxima in the thermopower are observed for y > $. If Ga,Te
is less likely to be characterised by heterocoordination in the liquid phase than In,Te,
the idea of a rigid band model so far as structure in a ( )is concerned is not valid.
In other words, although weak structure may appear in a ( E )as the composition Ga,Te
is approached, such structure will not be strongly in evidence at Ga2Te3. Thus, the
generic model will apply at Ga,Te3 and leads to a conductivity gap of 0.1 eV if a, -
is taken as 2900 R-' cm-' eV-'. An estimate made by Warren (1974) of the conductivity
gap in liquid Ga,Te3 (1.4 eV) appears totally inconsistent with the measured themo-
power. The structural and thermodynamic studies of Tsuchiya (1988) and Tsuchiya
et a2 (1982) provide further evidence that M2Te3+ M2Te+2Te is less likely for Ga,Te,
than it is for In,Te,.
6.3.4. Specific liquid semiconductors (broad dejnition). Many liquid alloys fall into this
category; they are characterised by heterocoordination, a positive d a / d T and a(EF),
which is not zero. Although the term liquid semiconductor has been taken to include
such materials, they are really semimetallic in character. If it were possible to cool
narrow definition liquid semiconductors to absolute zero, the Fermi function f(E )
would become sharp so that (+ would vanish. Broad definition liquid semiconductors
would not behave in this way and to this extent are apparently metallic. However, in
practice, the distinction between the two types of behaviour cannot be as clear-cut.
First, the finite value of A E for most narrow definition semiconductors closes rapidly
with temperature. For example, liquid T1,Te becomes a broad definition liquid semi-
-
conductor at 1000 K, i.e. at temperatures in excess of 270 K above the liquidus
temperature.
-
Secondly, since the width of dF/dE is kT, at the high temperature chzracteristic
of liquid semiconductors the behaviour of U ( ) below E, (or above E,) will, in most
cases, be sampled by the Fermi function. Thus, the observed transport parameters will
I I
-1 0 1 2
-&O0I
-600
-1 0 1
Ev-& lev)
Figure 79. The conductivity and thermopower derived from the a(E)shown in the inset:
(-) 1500 K and (---) 1000 K.
I I
Te 0.1 0.3 0.5 0.7 0.9 Ga

Y
Figure 80. The conductivity (950 "C)and the thermopower (e, 850 'C; A, 950 "C) for
liquid Ga,Te,-,. (data taken from Valiant and Faber 1974, Tschimer er al 1974).
show a smooth variation with temperature or composition as SE, (or SE,) approach
zero. This is well illustrated by the work of Gardner and Cutler (1977) on the magnetic
susceptibility of TI-Te alloys. The positive deviation from linear behaviour for ,y versus
becomes only gradually more marked at low values of a (figure 81).
For broad definition semiconductors, a ( E ) is likely to be strongly dependent on
y and T so that the inversion methods described in 0 6.3.3 will not be applicable. We
0 20 40
LT1/2 (n-1/2 cm-1/2 )
Figure 81. The magnetic susceptibility versus (conductivity)2 for a wide variety of liquid
Tl,Te,-, alloys (for symbol details see Gardner and Cutler 1977).
therefore limit our discussion to a few representative systems in order to show how
the general ideas discussed earlier in D 2 can be made quantitative.
6.3.4.1. Metal-metal compounds. The Li-Pb system represents an excellent example

of a broad definition liquid semiconductor. At or close to Li,Pb, v falls to a minimum
and S changes sign (figure 5 ) . This behaviour is consistent with the n ( E ) shown in
figure4. Further support for the basic model is provided by the Knight shift data of
van der Marel er al (1982) (figure 82), the magnetic susceptibility (Hackstein et a1
1980) and the Darken stability function (Saboungi er a1 1978). Another quantity, the
importance of which was first emphasised by Warren (1971), is the Korringa enhance-
mentfactor, T ~ This. measures a characteristic residence time of an electron near a
nucleus and becomes significant when deviations from NFE behaviour occur, such as
are expected for pseudogap or real gap alloys. The results shown in figure 83 for liquid
Li-Pb (a0=2300Q- cm-I) follow the expected trend, although rlK is, in comparison
with that for real gap alloys, still rather small (Warren 1977).
Many alkali-metal-based liquid alloys have a minimum conductivity at the
equiatomic composition, rather than at the octet compound (e.g. as in Li4Pb). A
good example of this type of behaviour is afforded by KPb (Meijer er a1 1986) where
a, is 1000 R-cm-. At this composition the Darken stability function is a maximum
(Saboungi ef a1 1986). The systematic work of van der Lugt and co-workers (see, for
example, Meijer et al1986) has established clear trends in the behaviour of alkali-metal-
Pb compounds, which are shown in table 1. Liquid Cs-Pb appears to be a borderline
liquid semiconductor and if the methods described in 0 6.3.3 are used (with a,=
1000 R-cm- eV- and r = 1) A E =Os Structural studies of alloys of this type are in
progress (Saboungi and Price 1989).
LI 20 LO 60 80 Pb
Pb (at%)
Figure 82. The Knight shift (in parts per million) for liquid LiiPb,-, alloys at the liquidus
temperature (van der Marel et a1 1982).
I I
Li 20 LO 60 80 F
Pb [at.%)
Figure 83. The Korringa enhancement factor for liquid Li! Pb,-,. alloys at the liquidus
temperature (van der Marel et a1 1982).
6.3.4.2. Chalcogen compounds. Most liquid tellurides and a few liquid selenides are
pseudogap materials, as the examples given in tables 1 and 23 illustrate. Liquid PbTe
has been investigated by Valiant and Faber (1974) and is an example of an alloy which
shows clear evidence for a p-n transition in the thermopower at stoichiometry (figure
84). In other liquid tellurides, for example Sb2Te, and Bi,Te,, the pseudogap is too
shallow for such a transition to occur and this fact is reflected by the smooth variation
with composition of the Knight shift and the magnetic susceptibility (figure 85). Such
Figure 84. The thermopower of liquid PbTe at 1223 K (Valiant and Faber 1974).
2 0
30 35 40 45
Sb, Bi concentration (at.%)
Figure 85. The magnetic susceptibility of Bi,.Te,-,. (640C) and Sb,.Te,-,. (670C)
(Uemura and Satow 1977).
behaviour is in sharp contrast with that for real gap liquids like T12Te,TlzSe and TIIS,
which show a clear diamagnetic maximum at stoichiometry (Uemura et al 1978b).
6.3.4.3. Transition-metal-chalcogencompounds. Several studies have been made on c

and S in a wide variety of transition-metal-chalcogen alloys (Laundy 1984, Barnes
1986, Okada and Ohno 1987). The results shown in figure 86 are largely due to Okada
and Ohno and agree well with those of other investigators. In particular, NiTe, Wise,
CoTe and FeTe are metallic, the high conductivity arising from the hybridised pjd
band. The shallow minimum in a ( y ) around CrTe, together with a positive dcr/dT,
indicates that this alloy is a pseudogap material. The data are incomplete for Ti-Te
and V-Te, but suggest that at stoichiometry VTe( ?) will be characterised by a pseudogap
and TiTe(?) by a real gap. The special cases of liquid CuTe, CuSe and MnTe have
been discussed in 0 6.3.3 and need not detain us further.
I I I I
- 1300 O C
0 20 40 60
Te [at.O h 1
Figure 86. The conductivity of a variety of transition metal tellurides (Okado and Ohno
1987).
6.4. The Hall coeficient

So far in this review little has been said about the Hall coefficient, R. The Hall
coefficient is considerably more difficult to measure than either U or S with the result
that much of the published data is inconsistent. We believe that the values of R shown
in table 31 are generally reliable, at least to within a factor of 2.
Table 31. The Hall coefficient for liquid semiconductors.
Liquid Broad/narrow Temp. R

semiconductor definition W) (cm3 C-') dlRl/dT Reference
CdSb 740 -8.0 x 10-5 -0 Enderby (1974)

ZnSb 820 -5.0 x 1 0 - ~ -0 Enderby (1974)
Bi,Te, 860 -8.7 x 10-5 -0 Enderby (1974)
SnTe 1090 -1.2 x 1 0 - ~ -0 Enderby (1974)
Cu2Te 1400 -5.3 x 10-3 -ve Glazov et al (1986)
Cu,Se 1400 -8.8 x -ve Glazov et a1 (1986)
cu,s 1400 -12.3 x 10-3 -ve Glazov et a1 (1986)
Tl,Te 800 -3.0x 10-3 -ve Enderby (1974)
Ga2Te3 1150 -1.0 x -ve Tschirner et a1 (1984)
In,Te3 973 -1.0 x 1 0 - ~ -ve Tschimer er a1 (1975)
As,Te, 690 -5 x 10-2 Andreyev and
Shlimak (1975)
A complete theory of the Hall coefficient in liquid semiconductors is not available

but the experimental results shown can be summarised in general terms. First, it is
found that R > Ro where Ro is the free electron value given by equation (I). Secondly
R remains negative even when E F approaches a conductivity gap from below E, and
in this respect differs markedly from the thermopower. Experimental data which
illustrate the dependence of R on chemical composition close to stoichiometry are
shown in
-32
-28 - I
rl
-24- 'I
I
- -20-
'T I
U
m I
5 -
7 -16
E
Q -12 -
-E -
-4
1
-
TI * i e ' '.--
0 1
Ballentine (1977) has demonstrated that the lowest-order correction to Rois at least
of third order in the scattering which means that the often quoted expression
(which in any case applies only in the degenerate limit) is incomplete. Nevertheless
the early measurements carried out on broad definition liquid semiconductors such as
liquid Te, Bi2Te,, and ZnSb were historically important because they were the first to
emphasise the essentially metallic character of such systems (Enderby and Walsh 1968).
As EF approaches a conductivity edge, the degenerate limit can no longer be used.
According to Ghibaudo (1987) the weak-field Hall coefficient is given in Kubo-
Greenwood formalism, by
where p ( E ) is the microscopic mobility.

In order to make further progress a functional form must be found for p ( E ) . In
the absence of any realistic theory, we write
--@I =(pc-Pc)+PXE -E d k
so that the Hall coefficient is given by
where p c , pc and p&are positive constants. The edge value for the Hall coefficient
can be readily found by setting EF= Ec = 0. This yields, after elementary manipulation
where the integrals .Iufkand I, are defined by equation (18). This expression is valid
for unipolar conduction in the conduction band; an equivalent expression for unipolar
conduction in the valence band can be obtained by replacing ac,pc and pc by a v ,
pv and pv, the sign of the Hall coefficient remaining negative. The Hall coefficient
for conduction in two bands derived from equation (26) follows the standard combina-
tion law
so that for the zero gap case with EF= Ec = Ev = 0

R = RcJ2
if the conduction is symmetric (i.e. a v = ac; PV=pc; p; = p&; p V = p c )
To obtain an experimental estimate of p, p and k, a series of experiments on a
unipolar conducting liquid such as MnTe is required. Unfortunately no systematic
study has yet been undertaken of this liquid because of severe experimental difficulties.
The best liquid available for estimates to be made is As2Te3(see Q 6.3.3) which appears
to be essentially a valence band unipolar conductor. The observed value of R is
- 5 x lo-* cm3 C-at a temperature (690 K) which corresponds to the edge value of
the thermopower. If k is taken as zero (the constant mobility approximation) and v
is unity, equation (28) simplifies to
R(edge) = - PV
avkT In 2
Thus for liquid As2Te, at 690 K, pv=2.1 cm2V-s-.
For liquid TI2Te, aV is 2900 R- cm- eV- so that at 800 K the value of R(edge)
-
is predicted to be - 1.6 x cm3C- if the same value for the microscopic mobility
is used. However for this liquid, ambipolar effects are important; thus at stoichiometry
-
a value -8 x cm3 C- is expected if all aspects of the conduction processes are
assumed to be symmetrical. The observed value is in fact nearer to - 3 x cm3C-
(figure 87) which suggests that the microscopic mobility for liquid T12Te is roughly
half that for As2Te3. There is clearly a need for a better understanding of the factors
which control p ( E ) at the microscopic level as well as systematic experimental studies
of R for a wide variety of liquid semiconductors.
7. Conclusions
This article has focused on the links between the structural and chemical aspects of
liquid semiconductors and their electrical properties. There is now little doubt that
finite conductivity gaps do exist in liquid semiconductors and arise from chemical
short-range order. In general the gaps are small and strongly temperature dependent
so that integration of the Kubo-Greenwood equations is necessary if the electrical
properties are to be properly understood. The simplified Boltzmann equations, though
often used in the past can lead to misleading conclusions. The chemical short-range
order is best probed at the partial structure factor level where departures from the
conceptually simple but extreme ionic model can be detected. It turns out that in
nearly all cases corrections to the simple model are necessary in order to account for
the structural data.
A simple inversion scheme has been proposed to extract the functional form of
a(E ) and the conductivity gap from experimental conductivity and thermopower data.
There is clearly a need to extend the method to a wide variety of liquid semiconductors,
particularly Ag,Se and Ag2S which have long been regarded as anomalous. It is of
particular importance to establish the composition dependence of the thermopower.
On the other hand, the unusual electrical properties of liquid Cu,X,-, for 0.67 > y > 0.5
(X = Te, Se) have now been satisfactorily explained in terms of the two (apparent)
valence states of copper. Similar considerations allow the composition dependence
of the thermopower of In-Te alloys in the range In2Te to In2Te3to be explained. In
all cases, detailed structural work to underpin the studies of electronic properties is
essential if further progress is to be made.
Acknowledgments
This article has benefited from discussions with many of our colleagues at home and
abroad and we specially wish to acknowledge helpful discussions with Professor Hensel
(Marburg), Dr Saboungi (Argonne), Professor Hoyer (Rostock) and Dr Evans (Bristol).
We owe a particular debt to Professor Cutler (Oregon) whose book Liquid Semiconduc-
tors has been a valuable source of information and ideas, and to Sir Nevi11 Mott
(Cambridge) for his sympathetic interest and guidance. Janet Wallace produced an
excellent typed version of our hand-written manuscript and we are deeply grateful for
her patience and skill, as we are to Felicity Hanley who completed the task on our
return to the UK. The Science and Engineering Council has provided financial support
for most of our work reported here and we are very grateful. The neutron diffraction
studies were largely carried out at the Institut Laue-Langevin (Grenoble) and we thank
the staff there, particularly Dr Chieux, for all their help.
References
Albers W and Haas C 1964 Proc. 7th Confi on Physics of Semiconductors (Pzris: Dunod) p 261
Alblas B P, van der Lugt W, Dijkstra J, Geertsma W and Van Dijk C 1983 J. Phys. F: Met. Phys. 13 2465
Allen J W, Lucovsky G and Mikkelsen J C 1977 Solid State Commun. 24 367
Anderson P W 1958 Phys. Rev. 109 1492
Andreyev A A and Shlimak I S 1975 Localisation and Metal-Insulator Transitions ed. H Fritzche and D
Adler (New York: Plenum) p 239
Ballentine L E I977 Liquid Materials 1976 (Inst. Phys. Conf. Ser. 30) p 188
Barnes A C 1986 PhD Thesis University of Bristol
Barnes A C and Enderby J E 1988a Z. Phys. Chem. Neue Folge 156 S529-35
-1988b Phil. Mrrg. B 58 497
- 1989 ILL Annual Report (Grenoble, ILL)
Bames A C, Laundy D and Enderby J E 1987 Phil. Mag. B 55 497

Bellissent R, Bergman C, Coelin R and Gaspard J P 1987 Phys. Rev. Leu. 59 66
Bellissent R and Tourand G 1980 J. Non-Cryst. Solids 35/36 1221
Bhatia A B and Thornton D E 1970 Phys. Reo. B 2 3004
Biggin S and Enderby J E 1981 J. Phys. C: Solid Stare Phys. 14 3129
-1982 J. Phys. C: Solid State Phys. 15 L305
Biggin S, Gay M and Enderby J E 1984 L Phys. C: Solid Stare Phys. 17 977
BEtry J 1978 Z. Nuturf: a 33 327
Brandow B H 1977 Adv. Phys. 26 651
Brinkmann P, Paulick C A, Elwenspoek M, von Hartrott M, Kiehl M, Maxim P and Quitmann D 1985
Phys. Lert. lllA 435
Busch G and Tieche Y 1962 Helv. Phys. Acta 35 273
Cabane C and Friedel J 1971 J. Physique 32 73
Catlow C R A and Stoneham A M 1983 J. Phys. C: Solid State Phys. 16 4321
Chaussemy G, Fomazero J and Laugier A 1980 J. Physique Coll. 41 C8 371
Chelikowsky J R and Burdett J K 1986 Phys. Rev. Lett. 56 96
Cohen M H,Soukoulis C M and Economou E N 1985 The Physics of Disordered Murerials ed. D Adler et
a1 (New York: Plenum) p 305
Copestake A P 1983 PhD Thesis University of Bristol
Copestake A P, Evans R, Ruppersberg H and Schirmacher W 1983 J. Phys. F: Mer. Phys. 13 1993
Copestake A P, Evans R and Telo da Gama M M 1980 J. Physique Coll. 41 C8 321
Cusack N E 1987 The Physics ofStrucruraZly Disordered Matter (Bristol: Adam Hilger)
Cusack N E and Kendall P W 1960 Phil Mag. 5 100
-1961 Phil Mug. 6 419
Cutler M 1977 Liquid Semiconductors (New York: Academic)
Cutler M and Field M B 1968 Phys. Rea 169 632
Cutler M and Mallon C E 1966 Phys. Rev. 144 642
Cutler M and Peterson R L 1970 Phil. Mag. 21 1033
Cutler M and Rasolendramitra 1985 Localisation and Metal-Insulator Transitions ed. H Fritsch and D Adler
(New York: Plenum) p 199
Dancy E A 1965 Trans. Metall SOC( A I M E ) 233 270
Ditman A V and Kulikova I N 1977 Sou. Phys.-Solid State 19 1403
Edeling M and Freyland W 1981 Ber. Bunsenges. Phys. Chem. 85 1049
Edwards F G, Enderby J E, Howe R A and Page D I 1975 J. Phys. C: Solid Stare Phys. 8 3483
Edwards F G, Howe R A, Enderby J E and Page D I 1978 J. Phys. C: Solid State Phys. 11 1053
Edwards S F 1962 Roc. R. Soc. A267 518
Enderby J E 1963 Proc. Phys. Soc. 81 772
Enderby J E and Bames A C 1973 Band Structure ofMetuls and Alloys (London: Academic) p 609
- 1974 Amorphous and Liquid Semiconductors ed. J Tauc (New York: Plenum) p 361
-1985 Phil. Mag. 52 363
Enderby J E and Collings E W 1970 J. Non-Cryst. Solids 4 161
Enderby J E, Cummings S, Herdman G J, Neilson G W, Salmon P S and Skipper N 1987 J. Phys. Chem
91 5851
Enderby J E and Gay A M 1980 J. Non-Cryst. Solids 35/36 1269
Enderby J E and North D M 1968 Phys. Chem. Liq. 1 1
Enderby J E, North D M and Egelstaff P A 1966 Phil. Mag. 14 961
Enderby J E and Simmons C J 1969 Phil. Mag. 20 125
Enderby J E and Walsh L 1965 Phys. Lett. 14 9-10
Evans R and Telo da Gama M M 1980 Phil. Mag. B 14 351
Faber T E 1972 Introduction fo the lleor): ojLiquid Metals (Cambridge: Cambridge University Press)
Faber T E and Ziman J M 1965 Phil. Mag. 11 153
Ferrante A, Li W and Tosi M P 1988 Phil. Mag. A58 13
Folmer J C W a n d Jellinek F 1980 J. Less-Common Met. 76 153
Franz J R, Brouers F and Holzhey 1980 J. Phys. F: Met. Phys. 10 235
Fritzsche H 1971 Solid State Commun. 9 1813
Fumi F and Tosi M P 1964 J. Phys. Chem. Solids 25 31
Garba E J D and Jacobs R L 1986 Physicu B 138 253
Gardner J A and Cutler M 1976 Phys. Rev. B 14 4488
- 1977 Liquid Materials 1976 (Inst. Phys. Conf. Ser. 30) p 466
Gaspard J P, Bergman C, Bichara C, Bellisent R, Chieux P and Goffart J 1987 J. Non-Crysf. Solids 97/88 1283
Gay M, Enderby J E and Copestake A P 1982 J. Phys. C: Solid State Phys. 15 4627
Geertsma W, Dijkstra J and van der Lugt W 1984 J. Phys. F: Met. Phys. 14 1833
Ghibaudo G 1987 J. Phys. C: Solid State Phys. 20 L769
Glazov V M, Chiztevskaya S V and Glagoleva N N 1969 Liquid Semiconductors trans. A Tybulewicz (New
York: Plenum)
Glazov V M, Koltsov V B and Kurbatov V A 1986 Sov. Phys. 20 889
Gopala Rao R V and Das R 1987 Phys. Rev. B36 6325
Greaves G N, Elliott S R and Davis E A 1979 Adv. Phys. 28 49
Guseinov A G, Yangirov A Y, Mamedov K K, Manedova K M, Mekhtiev M I and Gumbatov D 0 1986
Phys. Status Solidi a 93 K15
Hackstein K, Sotier S and Luscher E 1980 J. Physique Coll. 41 C8
Harrison W A 1959 Phys. Rev. 116 555
Hauffe K and Wagner C 1940 Z. Electrochem. 46 160
Hawker I 1974 Ph.D. Thesis University of Bristol
Hawker I, Howe R A and Enderby J E 1974 Proc. 5th Int. Con$ Amorphous Liquid Semiconductors (London:
Taylor and Francis)
-1978 Int. Con$ on the Electronic and Magnetic Properties ofLiquid Metals (Mexico) ed. J Keller (Mexico)
City: UNAM ) p 262
Heine V 1969 The Physics ofMetuls ed. J M Ziman (Cambridge: Cambridge University Press)
Hensel F 1982 Ionic Liquids, Molten Salts and Polyelecrrolytes (Berlin: Springer) p p 13-27
Hewaidy I F, Busmann E and Klemm W 1964 Z. Anorg. Allg. Chem. 328 283
Hikami S 1982 Proc. 4th Taniguchi Inf. Symp. Theory of Condensed Matter (Berlin: Springer)
Holzhey C, Brouers F, Franz J R and Schirmacher W 1982 J. Phys. E. Met. Phys. 12 2601
Hoyer W, Muller A, Matz W and Wobst M 1984 Phys. Status Solidi 84 11
Hoyer W, Muller A, Thomas E and Wobst M 1982 Phys. Status Solidi 72 585
Hoyer W, Thomas E and Wobst M 1975 Z. Nuturf a 30 235
Hoyer W and Tschimer H V 1983 Phys. Chem. Liq. 12 191
Huggins M L and Mayer J E 1933 J. Chem. Phys. 1 643
Huheey J 1983 Inorganic Chemistry (New York: Harper)
Hulliger F 1968 Structure and Bonding 4 83
Hurst C H and Davies E A 1974 J. Non-Cryst. Solids 16 343
Ilschner B B and Wagner C 1958 Acta Metall. 6 712
Ioffe A F and Regel A R 1960 Prog. Semicond. 4 238
Janz G J and Tompkins R P T 1980 J. Phys. Chem. Ref: Data 9 831
Kahl G and Hufner J 1988 Phys. Chem. Liq. 17 267
Kao S S and Cutler M 1988a Phys. Rev. 31 10 581
-1988b Phys. Rev. 38 9 457
Kazandzhan B I 1968 Sou. Phys. 2 329
Kazandzhan B I and Tsunikov A A 1974 Akad. Nauk SSSR 48 746
Kolomiets B T 1964 Phys. Status Solidi 7 359
Krebs H 1968 Fundamentals of Inorganic Crystal Chemistry (New York: McGraw-Hill)
Laugier A, Chaussemy G and Fomazero J 1977 J. Non-Cryst. Solids 23 419
Laundy D 1984 PhD Thesis University o f Bristol
Laundy D, Enderby J E, Gay M and Barnes A C 1983 Phil. Mag. 48 L29
Littlewood P B 1981 Phys. Rev. B 24 1710
Lucovsky G 1982 in The Physics of Selenium and Tellurium ed. E Gerlach and P Grosse (Berlin: Springer)
p 178
Marsh R E and Shoemaker D P 1953 Acta Crystallogr. 6 197
Martin W, Freyland W, Lamparter P and Steeb S 1980a Phys. Chem. Liq. 10 61
Martin W, Keita N M, Lamparter P and Steeb S 1980b Phys. Chem. Liq. 10 85
Matsuda H, Uemura 0 and Satow T 1985 Phys. Status Solidi a 90 77
Mayer J E 1933 J. Chem. Phys. 1 270
McGreevy R L and Mitchell E W J 1982 J. Phys. C: Solid State Phys. 15 5337
Meijer J A, Vinke G J B and van der Lugt W 1986 J. Phys. F: Mer. Phys. 16 845
Menelle A, Bellissent R and Flank A M 1987 Europhys. Lett. 4 705
Moss S C and Price D L 1985 Physics of Disordered Materials ed. D Adler et a1 (New York: Plenum) p 77
Mott N F 1969 Phil. Mag. 19 835
- 1982 Ionic Liquids, Molten Salts and Polyelectrolytes (Berlin: Springer) pp 1-9
-1987 J. Phys. C: Solid State Phys. 20 3075

Mott N F and Davies E A 1971 Electronic Processes in Liquid Semiconductors (Oxford: Clarendon)
Mott N F and Jones H 1936 The n e o r y o j t h e Properties of Metals and Alloys (Oxford: Clarendon)
Moustakas T D, Weiser K and Grant A J 1975 Solid Stare Commun. 16 575
Nakagima T, Uemera 0, Satow T and Yagihashi T 1982 Phys. Status Solidi b 112 311
Nakamura Y and Shimoji M 1973 The Properties of Liquid Metals ed. S Takeuchi (London: Taylor and
Francis) p 567
Newport R J, Howe R A and Wood N D 1985 J. Phys. C: Solid State Phys. 18 524
Nguyen V T and Enderby J E 1977 Phil. Mag. 35 1013
Nguyen V T, Gay M, Enderby J E, Newport R J and Howe R A 1982 J. Phys. C: Solid State Phys. 15 4627
Ninomiya Y , Nakamura Y an,d Shimoji M 1972 Phil. Mag. 26 953
Oberafo A A 1975 J. Phys. C: Solid Stare Phys. 8 469
Ohno H and Furakawa K 1981 J. Chem. Soc. Faraday Trans. I 7 7 1981
Okado T and Ohno S 1987 J. Phys. Soc. Japan 56 1092
Ovshinsky S R 1968 Phys. Rea. Lett. 21 1450
Paulick C A, Brinkmann R, Elwenspoek M, von Hartrott M, Kiehl M, Maxim P and Quitmann D 1985
J. Non-Cryst. Solids 77/78 1359
Phillips J C and Kleinman J 1959 Phys. Rev. 116 287
Popp K, Tschirner H U and Wobst M 1974 Phil. Mag. 30 685
Regel A R 1970 Roc.Int. Con5 Semiconductors (Cambridge, M A ) p 773
Reijers H T J, van der Lugt W and van Dijk C 1987 Physica B 144 404
Robertson J 1983 Phil. Mag. 47 L1
Rosen M, Nassif E and Kurlat H 1980 J. Physique Coll. 41 C8 356
Roth L M 1975 Roc.Int. Con$ on the Electronic and Magnetic Properties of Liquid Metals (Mexico) ed J
Keller p 344 (Mexico City: UNAM)
Rovere M and Tosi M P 1986 Rep. Prog. Phys. 49 1001
Ruppersberg H and Egger H 1975 J. Chem. Phys. 63 4095
Ruppersberg H and Reiter H 1982 J. Phys. F: Met. Phys. 12 1311
Saboungi M-L, Blomquist R, Volin K J and Price D L 1987 J. Chem. Phys. 87 2273
Saboungi M-L, Marr J and Blander M 1978 J. Chem. Phys. 68 1375
Saboungi M-L, Herron S J and Kumar R 1985 Ber. Bunsenges. Phys. Chem. 89 375
Saboungi M-L, Leonard S R and Ellefson J 1986 J. Chem. Phys. 85 6072
Saboungi M-L and Price D L 1989 Private communication
Sangster M J K and Dixon M 1976 Adl;. Phys. 25 247
Satow T, Ishikawa H and Uemura 0 1988 Phys. Status Solidi b 146 661
Schmutzler R W, Hoshino H, Fischer R and Hemel F 1976 Ber. Bunsenges. Phys. Chem. 80 107
Soltwi,;h M, Quitmann D, Ruppersberg H and Suck J B 1982 Ionic Liquids, Molten Salts and Polyelectrolytes
(Berlin: Springer) pp 136-41
Strange P and Barnes A C 1985 J. Pbys. F: Mer. Phys. 15 L263
Suzuki K 1976 Ber. Bunsenges. Phys. Chem. 80 689
Takeda S, Tamaki S and Waseda Y 1983 J. Phys. Soc. Japan 52 2062
-1984 J. Phys. Soc. Japan 53 3830
Takeuchi S and Endo H 1961 Trans. Japan. Inst. Met. 2 243
Thomas P 1975 J. Non-Cryst. Solids 77/78 121
Tieche Y 1960 Aelu. Phys. Acta 33 963
Tourand G and B r e d M 1971 J. Physique 32 813
Tourand G,Cabane B and Breuil M 1972 J. Non-Cryst. Solids 8-10 676
Tschimer H-U, Popp K and Wobst M 1974 Proc. Con$ on Amorphous Semiconductors (Reinhardsbnmn
DDR) p 354
Tschirner H-U, Uhlig K and Wobst M 1984 Phil. Mag. 50 645
Tschimer H-U, Wolf R and Wobst M 1975 Phil. Mag. 31 237
Tsuchiya Y 1988 J. Phys. Soc. Japan 57 2425
Tsuchiya Y , Takeda S, Tamaki S and Seymour E F W 1982 J. Phys. C: Solid State Phys. 15 649
Uemura 0, Itoh M and Satow T 1982a Phys. Status Solidi b 109 361
Uemura 0, Sagara Y, Munro D and Satow T 1978a J. Non-Cryst. Solids 30 155
Uemura 0, Sagara Y, Tsushima M, Kamikawa T and Satow T 1979 J. Non-Cryst. Solids 33 71
Uemura 0 and Satow T 1977 Phys. Status Solidi b 84 353
Uemura 0, Satow T, Abe I and Oto T 1978b Phys. Chem. Liq. 8 157
Uemura 0, Segawa M and Satow T 1982b Ber. Bunsenges. Phys. Chem. 86 1145
Uemura 0, Takahasi K and Satow T 1983 Ber. Bunsenges. Phys. Chem. 87 56

Valiant J C and Faber T E 1974 Phil. Mag. 29 571
van der Lugt W and Geertsma W 1987 Can. J. Phys. 65 326
van der Marel C, Geertsma W and van der Lugt W 1982 J. Phys. F: Met. Phys. 10 2305
Vetter F A and Kubaschewski 0 1953 Z. Electrochem. 57 243
Warren W W 1971 Phys. Rev. B 3 3708
-1974 Proc. 5r!1 Int. Con$ on Amorphous Liquid Semiconductors (London: Taylor and Francis)
- 1977 Liquid Metals 1976 (Inst. Phys. Conf. Ser. 30) p 436
Waseda Y 1971 Prog. Mater. Sci. 25 1
- 1984 Novel Applications of Anomalous (Resonance) Scattering for Structural characterisation of Dis-
ordered Materials (Berlin: Springer)
Waseda Y and Tamaki S 1975 2.Naturf: a 3 0 1655
Weast R C 1975 Handbook of Chemistry and Physics (Florida: CRC)
Weber M, Steeb S and Lamparter P 1979 2.Natutf a 3 4 1398
Welland M E, Gay M and Enderby J E 1985 Physics of Disordered Sysrems, ed. D Adler et a1 (New York:
Plenum) p 695
Wells A F 1984 Strucrural Inorganic Chemistry (Oxford: Clarendon)
Wilson E G 1962 Phil. Mag. 7 989
Wilson J A 1972 Adu. Phys. 21 143
Woodcock L V and Singer K 1971 Trans. Faraday Soc. 67 12
Zaanen J, Sawatsky K A and Allen J W 1985 Phys. Rev. Lerr. 55 418
Zallen R 1983 7he Physics of Amorphous Solids (New York: Wiley)
Ziman J M 1961 Phil. Mag. 6 1013

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Home Search Collections Journals About Contact us My IOPscience

1990 Rep. Prog. Phys. 53 85

Please note that terms and conditions apply.

J E Enderbyf and A C Barnes?

This review was received in February 1989.

0034-4885/90/020085 + 96$14.00 0 1990 IOP Publishing Ltd 85

2. The three regimes of conductivity

where f is the Fermi-Dirac function and EF is the Fermi energy?.

f In the merallic approximation af/aE is replaced by a sharp function centred on E , so that

First, it broadens the Fermi function so that, even for a temperature-independent

'conductivity gap', a concept to be explained later. It should be emphasised that the

1200 1250 1300 1350

3. Chemical short-range order in liquid alloys

Table 1. The liquids discussed in this article. M = metallic, B = liquid semiconductor

Liquid Classification* Temp. ( K ) U (a- cm-I) duldT

or, since k o = 2 r / A o , k = (477- sin @ / A o ) where ho is the incident wavelength and 0 is

where p is the total number density.

Table 2. Examples of coherent scattering lengths (fm) ( 1 fm = IO-%).

Element or Element or Element or

Ti 1.87 63cu 6.7 Te 5.80

3.3. Hard-sphere liquids

interatomic potentials becomes a relevant length scale in determining the overall

3.4. Ionic melts

with a,p =+,-.

property of charge cancellation for r b 5 A. This effect, first emphasised by Woodcock

Table 3. Near-neighbour distances in molten salts.

Table 4. Coordination numbers.

MgCI, 0.66 4.3 4.1 6

3.5. Covalently bonded solids

3.6. Transition metal chalcogenides

3.7. Mass transport

Table 5. The viscosities of some liquids close to the melting point.

Liquid 7l(cP) Predominant bonding type

Self-diffusion coefficients for a selection of liquids are shown in table 6 , again at

4. The structure of liquid semiconductors

4.2. Elemental liquid semiconductors

Figure 18. A single chain in the trigonal form of Se.

Se 2.37 3.43 1.45 102" 50'

Figure 24. The structure of rhombohedral arsenic (Greaves et a1 1979).

Table 8. The structure of liquid Te by neutron diffraction:

Hawker et a1 (1978) 773 2.80 4.10 - No

4.3. Binary liquid semiconductors [narrow dejnition)

Table 9. The structure of liquid Ag,Te.

Interatomic Observed Calculatedt Solid state$

0 0.4 0.8 1.2 1.6

Table 10. The structure of liquid Tl,Te.

Interatomic Observed Calculated?

Table 11. Structure of liquid and solid T1,Se.

Liquid 3.40 7.4

differences. There is no feature corresponding to a peak in gcucu(r ) at 2.9 A, which -

Table 12. The structure of Cu,Se.

Ideal crystal 2.50 2.88 4

apparent coordination numbers fiCsAu or figsAuobtained directly from integrating G(r )

Table 13. The structure of liquid and solid CsAu.

Liquid 3.57 -81

7 Penetration effects mean that this value is an upper bound.

Although in principle the structure of Mg3Bizcan be probed at the partial structure

Table 14. The structure of solid and liquid Mg,Bi,.

Liquid 3.00 -6 (average)

Table 15. The structure of solid and liquid In,Te,.

Liquid 2.95 -3 (average)

4.4. Binary liquid semiconductors (broad definition)

Table 16. The structure of liquid Cu,Te.

Interatomic Observed Calculated?