ON THE STRUCTURAL, THERMAL, ELECTRICAL,

AND MAGNETIC PROPERTIES OF AuSn*

J.-P. J A N ,W. B. PEARSON,
Division of Pure Physics, National Resea~cltCoz~ncil,Ottawa, Canada
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A. KJEI~SHUS
Che~nicalInstitute A , Unioersity of Oslo, Blindern, Norway

S. B. WOODS
Depa~tnzentof Physics, University of Alberta, Ednzonton, Canada
Received September 9, 1963

ABSTRACT
T h e Aul-,Sn phase has a homogeneity range within the limits 50.0 a n d 50.5
at.% Sn. T h e lattice constants a n d observed densities vary between the limits:

The thermal conductivity, electrical resistivity, and absolute thermoelectric

power of oricnted single crystals of Aul-,Sn have been measured between 2.5" I<
For personal use only.

and room temperature. T h e results exhibit pronounced anisotropies. R/leasurements

of the magnetic susceptibility between liquid air temperature and 650-750" K
are also reported for three different Aui-,Sn alloys.
T h e various results are discussed, and somc speculations are presented regard-
ing the number of conduction electrons in AuSn.

INTRODUCTION
T h e AuSn phase appears first to have been prepared by Matthiessen (1860),
and its occurrence was later inferred from electromotive force measurements
of gold-tin alloys by Laurie (1892, 1894) and Puschin (1908). Vogel (1905)
confirmed its existence by a thermal and microscopic study of the gold-tin
phase diagram. For further references to earlier studies of the gold-tin system,
see Gmelins (1954).
T h e crystal structure of AuSn was determined from single-crystal and
powder X-ray studies by Preston and Owen (1927), who showed it to have a
structure of the NiAs, B81 type. T h e lattice constants of AuSn were also deter-
mined by Stenbeclc and Westgren (1931) and Bottenla and Jaeger (1932).
The distribution of gold and tin atoms in nlolten AuSn alloys was studied by
Mendus (1947) using X-ray diffractioll. Compared with a purely statistical
distribution of the two kinds of atoms, nlolten AuSn exhibits a relatively high
degree of short-range order.
T h e magnetic susceptibility of various gold-tin alloys was nleasured a t
roolll tenlperature by Spencer and Jolln (1927). Although these authors did
not investigate a 50.0 a t . % Sn alloy their results indicate that AuSn is dia-
magnetic.
"Issued a s N.R.C. No. 7614.
Canadian Journal of Physics. Volume 41 (1963)

2252
 JAN ET AL.: PROPISRTIES OF AuSn 2253

Matthiessen (1860) showed AuSn t o have metallic electrical conductivity

a t room temperature, and measurements of the resistivity a t various tempera-
tures between 1.43 and 20.43' I< were made by d e Haas et al. (1930) and b y
Allen (1933; see also NIcLennan et al. 1932) in their search for superconduct-
ing compounds. T h e absence of superconductivity has been discussed by Forrer
(1937).
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T h e thermodynamic properties of AuSn were studied by several authors.

I-Ieat capacities (Bottema and Jaeger 1932; Kubaschewski 1943) from room
temperature to 908' I< and the latent heat of fusion (I<ubaschen~sl;i1943) were
evaluated from measurements with a drop calorimeter. T h e heat of formation
was obtained by Biltz et al. (1934) from the heats of solution in Brz-I<Br/aq.,
Rrz-HBr/aq., and IC13/aq. and by Kleppa (1950) from electroinotive force
measurements. Recently a mass spectrometric technique has been employed
b y Ackerman et al. (1962) to deduce the dissociation energy of gaseous AuSn
molecules.
Reference can be made t o the reviews of Jellinek (1959) and I<jel;shus and
Pearsoil (1963) for recent general surveys of the properties of phases with the
NiAs and closely related structures.
T h e present investigation was undertalcell to gain such information about
the nature of the chemical bonds in the AuSn phase a s the number of electrons
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partaking in bonding, the band structure, and the shape of the Ferrni surface.
This compound is especially interesting because it is the only known phase with
the NiAs structure t h a t does not contain a transition metal in combination with
a metalloid or B Group atom, and therefore a study of this single exception,
AuSn, may throw light on the many compounds with the NiAs structure.
This work has been greatly stimulated by the discovery that we could obtain
strong d e I-Iaas - van Alphen oscillations in the magnetic susceptibility of
single crystals of AuSn (Recl; et al. 1963), since in principle this allows the
geometry of its Ferlni surface to be determined experimentally. In the present
paper we report structural and magnetic data together with the electron
transport properties of AuSn (the interesting anisotropy in the tl~ermoelectric
poxver has already been referred to briefly by Jan and Pearson 1963) \vIlile
\vorl; on the interpretation of d e - v a n Alphen data proceeds.

EXPERIMENTAL NIETHODS
Au-Sn alloys were prepared in evacuated glass or silica tubes from "spec-
pure" tin (Johnson, Matthey & Co.) and specially purified gold (kindly placed
a t our disposal by Dr. 2.S. Basinski) or "spec-pure" gold (Johnson, iVIatthey
& Co.). A variety of slow-cooling and zone-refining neth hods were used in the
preparation of single crystals. Results on four snmplcs (I-IV) of nominally
equiatomic composition will be discussed, a s well as of several alloys with
slightly different compositions. "Equiatomic" samples I , 11, and I11 con-
tained an occasional s ~ n a l globular
l inclusion of a differeilt phase.
T h e X-ray photographs of the samples mere taken in a Guinier focusing
camera of SO mm diameter with strictly monocl~romatizedCuI<al radiation.
For the cnlculation of lattice constailts by the Guinier method, potassium
 2254 CANADIAN JOURNAL O F PHYSICS. VOL. 41. 1963

chloride (Analar, T h e British Drug I-Iouses Ltd., a = 6.2919 A ; Hambling

1953) mas added as an internal standard. Lattice constailts are expressed in
Angstr6m units on the basis of,,,X,c = 1.54050 A.
Crystals were cut and ground into rectangular bars for electrical measure-
ments by methods t o be described by Beck (1964). Single-crystal alignnlent
was carried out by standard X-ray methods.
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The density of the samples was determined by the pycnometric method a t

25" C with kerosene as displace~nentliquid. T o remove gases adsorbed by the
sample, the pycnoineter was filled under vacuum with kerosene. Each sample
weighed between 5 and 7 g.
Magnetic (i), thermoelectric (ii), electrical and therlnal conductivity (iii)
studies mere made by methods standard in our laboratories (cf., e.g., (i)
Curie method: I-Ieyding et al. (1961) ; Gouy method: Gr$nvold and Jacobsen
(1956); (ii) Christian et al. (1958); (iii) White and Woods (1955; see also
White 1959)).

RESULTS
1 . L i m i t s of Homogeneity
Lattice parameters of five alloys ranging in colnposition froin 47.4 to 52.4
at.yo Sn established the range of homogeneity of the AuSn phase as approxi-
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inately 50.0 to 50.5 a t . yo Sn in alloys annealed for three days a t 290" C and
quenclled in ice water (Table I and Fig. I ) . A similar result was obtained
froill nlicroscopical examination of alloys annealed for three days a t 380' C
and quenched in ice xvater. X-ray densities calculated on the assumption of
I I I I I I I I I I I
I I
-0
- 5.522

-- - 5.520 .c
U
4.322 - -& - 5.518
0-
4.320 -
- 5.516

-
--
4.318
oQ
-
C
4.316 -
I
I
4.314 - I
I p 0-
I 1
4.312 - "B-Au., Sn" + Aul-~Sn -lAu,-,Snl-
I I
nul-,Sn t AuSnz
; ;
I I I I I I I I I I I
48 49 50 51 52
ATOMIC % Sn
FIG.I . Variation in lattice constantsof the Aul-,Sn phase with tin content in alloys quenched
from 290" C.
 JAN ET AL.: PROI'ERTIES O F AuSn 2255

TABLE I
Lattice constants and observed and calculated densities of the ALII-,S~phase

Sample
Nominal Density (g/cm3)
composition, -
at. % Sn Material a (A) c (A) cia Dwcn D x - ~ ~
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50.00 b\uSn(I), pure end of 4.3201 5.5222 1.2783 - 11.741

zone-refined ingot
(start)
50 .OO rluSn(I), middle of zonc- 4.3207 5.5226 1.2782 11.739 11.741
refined ingot, near the
top
50.00 AuSn(I), middle of zone- 4.3194 5.5203 1.2780 - 11.749
refined ingot, near the
bottom
50.00 :\uSn(I), impure end of 4.3230 5.5234 1.2777 11.811 11.723
zone-refined ingot
50.00 :\uSn(II), single crystal 4.3213 5.5228 1.2780 11.717 11.734
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subtraction of gold atoms with change of conlposition from Aul.ooSn to

A u ~ , are~ ~in Sreasonable
~ agreement with pycnometric density measurements
made a t 25' C. (They do not, however, agree if the X-ray densities are calcu-
lated on the assulllptioll of substitution of Au by Sn, or of addition of Sn
atoms.) AuSn, therefore, has a limited range of subtractiollal solid solutioll and
the phase can be designated Aul-,Sn (0.00 < x <
0.02). X-ray photographs
of annealed two-phase alloys confirmed that the neighboring phases are
"P-Au4Sn1'on the one side and AuSnz on the other.
As a matter of interest, the cornposition of various portions of a zone-
purified AuSn ingot (sample I , more than 15 passes) was studied by lattice
parameter lneasurenlents with the results given in Table I. The start and
middle portions ((i) near the top, (ii) near the bottom) of the ingot corre-
spond to 50.10, 50.04, and 50.15 at. % Sn respectively, whereas the final end,
presulnably containing the impurities, has a lattice parameter lying beyond
the range obtained for pure binary Aul-,Sn alloys (Fig. I). There is also a
corresponding discrepancy between DDy,, and Dx-,,, for the final end when
the latter is calculated as previously, but assuming a pure binary alloy. The
middle portion of this ingot (I) was used for electrical conductivity (Fig. 5)
and nlaglletic susceptibility measurements (Fig. 6); the middle portion of
ingot I1 used for electrical nlcasurements (Figs. 4 and 5) corresponded to a
compositioll of 50.02 at. % Sn, determined from the lattice parameter curves
(Fig. 1).
2. Crystal Structure
The structure deternlillation of Preston and Owen (1927) indicated a NiAs
+
arrangement with 2 Au in (a) 0, 0, 0 ; 0,0, and 2 Sn in (c) f+,3, t of
 2256 C A N A D I A N JOURNAL O F PHYSICS. VOL. 41, 1963

space group PG3/mmc (D;,,). Since an anti-NiAs arrangemcut with the atoll1
positioils reversed would also be possible and the earlier structure determina-
tion was based on some si~llplifyi~lg assu~llptio~ls,we have co~npareclanew the
observed and calculated i~lte~lsities of powder reflections, with I-csults con-
fir~ningthe earlier work.
The intensities of the reflectio~ls were calculated with the formula
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I, = IF/" Lp Xv, applying 110 correctio~ls for absorption or te~nperaturc

factors. The calculatioil of the F values was ~iindein terms of both a NiAs
and ail anti-NiAs structure ~ilodelfor AuSn.
The relative intensities, l o , of the reflectioils 011 the powder photographs
tirere deter~llinedfro111photometer recordi~igsof the films. Multiple-film photo-
graphs were used to avoid errors in the estinlation of the highest and weakest
i~lte~lsitieson the photographs. The observed intensities were referred to a
relative scale by making the sums of I, and 1 0 equal.
The statistical test R = C[I,- I,l/ CIo agreed much better with the pro-
posed NiAs inodel (R = 0.105) than with the model assumi~igthe anti-NiAs
arrangeine~lt(R = 0.385). For the two sets of I, values
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The reliability indices together with the individual I, values leave 110 doubt
about the correctness of the NiAs structure assumed earlier.
3. Thermal Condz~ctivity
i\/Ieasurernents of thermal conductivity, I ( , have been inade between 2" and
40" I< on four specimens cut from AuSn 111 (see Fig. 2), and a t the same
time the electrical resistance of the specimens was measured using the ther-
nloineter connections as potential leads.
These electrical resistivity measurements are not regarded as reliable below
about 6" I<, because below this temperature stepwise decreases of resistivity
\Yere noted, which were not identical in different experi~uents.:Is no corre-
sponding changes were ever seen in the thermal conductivity I-esults, this
peculiarity was attributed to a thin layer of conta~nination that became
superconducting over part of the specimen surface. This behavior was ilever
fouild in resistivity measurements made during thermoelectric ~neasureme~~ts
or in separate experiments for measuring the resistivity (data such as those
shown in Fig. 6).
The four samples were oriented single crystals cut from a large crystal
growl1 from a seed in a sealed evacuated glass tube. 'The crystal co~ltai~led a
very few globular inclusio~lsof a second phase.
Calculations of the Lorenz number, L = p ~ / T ,fro111 the ~ileasured data
show that a considerable proportion of the heat in AuSn is carried by lattice
waves. At low teinperatures L = 3 X watt ohni deg-2 and above 8" K it
decreases gradually, but is still greater than the So~nmerfeldvalue L, = 2.45
X watt ohm deg-2 a t 30" I<. If all the heat were conducted by electrons
the Lorenz ilunlber should have the Sommerfeld value below -8' K, where
 JAN ET AL.: PROPERTIES O F AuSn
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FIG.2. Thermal conductivity of four single-crystal rods of AuSn 111 a s a function of tem-
perature. T h e orientation of the crystals is indicated on the diagram.

the electrical resistance becomes sensibly constant and impurities are the only
important electron scatterers; at higher temperatures it should pass through
a minimum but should never exceed the Sommerfeld value unless lattice con-
ductioil is present. If we assume that K is composed additively of the electronic
conductivity, K,, and the lattice conductivity, K ~ ,then below 8" K where
K, = L,Tlpo we can calculate K,. At 8" K, rc, is about 20% of the total con-
ductivity and it decreases possibly as fast as T2as the teillperature is lowered.
The temperature variation is uncertain because of the sn~allnessof K,, but
scattering of the lattice waves by electrons or by dislocations, which should
be dominant at these temperatures, is consistent with a T2 variation.
At temperatures above 8" K, the temperature variation of K, cannot be
predicted with any certainty, and lattice wave scattering of the electrons also
becomes important, so that K, is no longer proportional to the temperature.
I t is not possible, therefore, to separate the conductivity components nor to
assess the relative effectiveness of the different scattering mechanisms.
 2258 CANADIAN JOURNAL OF PHYSICS. VOL. 41. 1963

4. Electrical Properties
The ilotable anisotropy ill the absolute thermoelectric power arid electrical
resistivity of AuSn has already been reported briefly (Jan and Pearson 1963)
and thermoelectric results talien fro111 that paper are reproduced in Fig. 3.
These measurements were made on the oriented single-crystal specimens of
AuSn I11 subsequently used in thennal conductivity studies.
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The most striking feature of the curves shown in Fig. 3 is the strong positive
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a TEMPERATURE (OK)

b TEMPERATURE ( O K )

FIG.3. Absolute thermoelectric power of four single-crystal rods of AuSn I11 as a function
of temperature. The orientation of the crystals is indicated on the diagram. X marks points
calculated with equation (2) using measured values of thermal conductivity.
 J A N BT AL.: PROPERTIES O F AuSn 2259

phonon drag contribution t o the thermoelectricity (reaching a ~naximuma t

about 25' I<) of samples whose axes lie in the basal plane (nb), and its near
absence in samples oriented along the c axis. The positive phonon drag therlno-
electricity shows a nlarlted decrease in size as the residual resistivity of the
samples increases, as indicated in Fig. 4. Such behavior could well be expected
from the character of the Aul-,Sn solid solution, because the size of the
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phonon drag contribution a t low temperatures (say < 3 8 ) depends particularly

on the scattering of phonons by impurity atoms, since this in effect reduces
the fraction of "phonon 111omentu111" transferred to the conduction electrons
or holes. T h e effectiveness of phonon scattering by impurity ato~llsin the
lattice depends in the first place on the mass ditierence of the inlpurity atoms
from those of the matrix, so that vacancies in the Au sites of the AuSn structure,
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FIG. 4. Absolute thermoelectric power of three single crystal rods of AuSn 11, 111, and
IV a s a function of temperature. (Specimen axis close to [loo].) T h e residual resistance ratios
of the samples, RJ.?/(R?96-R4.2),in units of are indicated on the diagram, as a n approxi-
mate measure of purity or stoichiometry.
 2260 CANADIAN JOURNAL O F PHYSICS. VOL. 41, 1963

which occur over the 1/2 at. % range of subtractional solid solution, should
cause a large change in phonon scattering. If, therefore, the increasing residual
resistivity of the samples shown in Fig. 4 results from increasing numbers of
vacancies on gold sites as the composition of the samples becomes Sn-rich,
then the accompanying decrease in phonon drag thermoelectricity is well
accounted for. Lattice parameter measurements for the samples (Table 11)
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do indeed confirm this picture.

TABLE I1
Residual resistivity, lattice constants, and estimated composition (from Fig. 1) for
AuSn 11, AuSn 111, and AuSn IV (see Fig. 4)

Estimated
~ 4 . I<
2 ~ composition
Sample number pmaDI<-P4.?O I< a (A) c (A)
--
in at.% Sn
! \ U S ~I1 35.0X10-3 4.3214 5.5225 50.03
AuSn 111 83.SX10-3 4.3209 5.5222 50.06
AuSn IV 150.6XlO-3 4.3198 5.5215 50.12

The thermal conductivity measurements (Section 3) now permit a proper

test of the Thornson-Voigt law for thermoelectricity t o be made. For a
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uniaxial (hexagonal) crystal with isotropic thermal conductivity the electrical

resistivity and the absolute thermoelectric power should follow the relation-
ship

where X[lool, Xlooll, and X(+)represent either the electrical resistivities ( p )

or the absolute thermoelectric powers (S) measured along rods cut parallel
+
to [loo], [OOl], and to a direction malting an angle with [OOl]. If, as might
be expected for a uniaxial crystal, the thermal conductivity is a~zisotropic,
then the experimental conditions are such that the directions of temperature
gradient and thermoelectric measurement (along the sample axis) no longer
necessarily coincide. Under these conditions a correction term (cf. Stabler
1934; I<ohler 1941) must be included in the Thomson-Voigt formula (1) for
the thermoelectric power which relates the anisotropy of the thermal con-
ductivity to the crystal orientation. The Thomson-Voigt law then becomes

(Sroo~l- S [ I O O
(k-
~ ) 1) cos2+ sin2+
(2) S(+) = Sriool sin2++~loollcos2+-t- k cos2++sin2+ 9

where k = ~ [ 0 0 1 ] / ~ [ 1 0 , ) ]describes the anisotropy of the thermal conductivity. If

the measured a~lisotropyof thermal collductivity a t low temperatures is taken
into account with (2), the agreement between the predictions of the Thomson-
Voigt law and the experimental results shown in Fig. 3 is improved (cf. Jan
and Pearson 1963).
Although the four samples used in these experiments were cut from the
same large single crystal, there are bound to be slllall random differences of
purity and composition among them. At the lowest temperatures ( < l o 0 I<)
 JAN ET AL.: PROPERTIES O F AuSn 2261

when impurity scattering dominates both the electrical resistivity and

diffusioil therinoelectricity, we may expect the Thomson-Voigt law not to
hold because of these arbitrary differences of con~position.T h e measurements
shown in Fig. 3 indicate that this is the case for the tl~ermoelectricpower
below about 10" I< a i d a corresponding result is shown in Table I11 for the
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TABLE I11
Electl-ical resistivity data for AuSn single crystals-Observed
xalues of (ptos-pj) a n d ~4.2,and values calculated by the
Thomson-Voigt law from data for + = 0" and + = 00"

Orientation ( P ? O S - -O P
~ S~
,) (~?9~-~d)cnicl
d, ohm cm ohm C I ~

90" a 12.0
GOo 30' off a 13.2 13.4 ( < 2 y 0 )
200 200 ori c 16.7 16.9 (<2%)
0 c 17.6
PI.? obs P4.2 on10
90" a 1.11
GO0 30" orf a 1.1s 1.18 (=)
20" 20" off c 1.16 1.36 (-17%)
0 c 1.40

electrical resistivity measurements. T h e Thornson-Voigt law for electrical

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resistivity is obeyed to within 2% for thermal scattering (pld = p2~~oIC-P40K)l

which should scarcely be influenced by minor variations of composition, but
not for impurity scattering (p~.zoIc). The absolute accuracy of the resistivity
measurements is, however, not too great because of uncertainty in deter-
mining the effective length between the potential contacts of the rather short
crystals examined.
Typical electrical resistivity - temperature curves for AuSn samples are
shown in Fig. 5. The temperature coefficients,

calculated for the linear portions of the curves give a = (2.60Zk0.08) X10-3
" C-I for all specimens (and orientations) which we have measured. Using a
Griineisen function, the approximate values of 8, (at a telnperature near 8)
obtained from the resistivity curves are 90" K in the [loo] direction and 120" I<
along [OOl]. Since, for a n isotropic metal, 8, is not expected to differ greatly
from OD a t temperatures near 8 (Kelly and iflacDonald 1953; see also I<elly
1954), i t is seen that the maxi~numin the thermoelectric power (25Zk5" I<,
Figs. 3 and 4), resulting from the temperature dependence of the phonon
drag thermoelectricity, occurs close to a temperature of 8,/5, as noted in
several other lnetals and alloys (cf. e.g. Pears011 19G2).
The I-Iall coefficient (R) of AuSn salnple I1 is - 18.4 X 10-5 cm3/coulomb
a t room temperature, corresponding to an average number of 1.5 electrons
per n~olecular unit AuSn according to the free-electron theory. I n AuSn,
therefore, the Hall coefficient and the diffusion tl~ermoelectricpower both
have the same (negative) sign, indicating dominant electron conductivity.
 CANADIAN JOURNAL O F PHYSICS. VOL. 41. 1963

22
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TEMPERATURE IN "K

' I . 5. Typical electrical resistivity 111easurcments as a function of temperature for various

AuSn sa~ilples. ]Vote: Thermoelectric contacts were used for these measurements a n d the
elfective sample length is here dctermined less precisely than in the data of Table 11.

Nevertheless, it s h o ~ ~ l be
c l noted t h a t this correspondence of sign is not neces-
sarily t o be expected in metals (cf. e.g. copper, Gold et ul. 1960).
5. Mulag~zeticProperties
T h e magnetic susceptibilities of alloys with co~llpositio~lsAul,ooSn, Auo.99Sn,
and Auo 98Sn are sho\vn as a function of temperature in Fig. 6. T h e Aul-,Sn
phase is diamagnetic a n d the susceptibilities of the three samples increase
linearly with increasing temperature below the melting point. T h e stoichio-
metric sample mas heated to a temperature of 725" I<, ivl~ich is
above the melti~lgpoint where the susceptibility increases sharply a s the
sample melts. T h e susceptibility-temperature relation below the melting point
indicates t h a t the Au0.99S11 and A ~ o , ~ &samples
n may also be represented
by a curve si~nilart o t h a t of the A U , . ~ ~ Ssample
II during melting.
T h e total susceptibility is the sum of t h e lattice susceptibility xL a n d the
susceptibility of the free charge carriers xc. xL is the susceptibility of any
 JAN ET AL.: PROPERTIES O F AuSn 2263
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TEMPERATURE (OK)

FIG.8. The magnetic susceptibility of the Aul-,Sn phase a s a function of temperature. T h e

filled circles 011 the diagram correspo~ldt o data obtained by the Curie method (Heyding a n d
Bennett), whereas the open sy111bolsrepresent susceptibilities (mean values) obtained by the
Goup method. T h e following equations of the straight lines have been determined by the
method of least squares:

in the temperature range 90" t o 600° I< (units e.m.u./g). T h e probable error in the esperi-
mental points is approximately +0.001?X c.m.u./g.

localized valence electrolls and the energetically lower lying electronic levels
associated with the cores of the gold and tin atonls (cf. Busch and Mooser
1953). The carrier contribution xc consists of two parts, a dialnagnetic con-
tribution xo resulting from the orbital notion of the carriers and a para-
magnetic contribution x,, that is approximately three times larger than xo,
resulting from the spin of the carriers. For nonlocalized states, the former is
usually interpreted with the Landau-Peierls relation and the latter by the
Pauli theory (cf. i\iIott and Jones 1936). Such individual contributions to the
observed susceptibilities are difficult to account for without a detailed knowledge
about the nature of the chemical bonding and the geometry of the Ferlni
surface. The positive temperature coefficient of the susceptibility indicates over-
lapping bands, because the transfer of electrons between two bands increases
both the number of holes in the lower band and the number of electrons in
the upper band.
 2264 CANADIAN JOURNAL O F PHYSICS. VOL. 41. 1963

The observed diamagnetic susceptibility clearly shows that no electrons

with unpaired spins are present in the d shells of the gold and tin atoms.
Assuming, therefore, that a maximum number of five electrons (one from Au
and four from Sn) partake in chemical bonding, we have estimated the value
of the magnetic susceptibility of A U ~ .for~ 5,
S 3,
~ or 1 free electrons (4 and 2
are unlikely) as follows: The diamagnetic contributions due to the cores of
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gold and tin atoms according to Iclemm (1941) are -40X10-6 e.m.u. per
mole Au+ and - 1GX lopGand -20X e.m.u. per mole of Sn4+ and Sn2+
respectively. The contribution of x, resulting from the localized valence band
electrolls has been calculated as described by Busch and Mooser (1953). The
carrier contribution xc is, according to NIott and Jones (193G),

where p is the density, A half the molecular weight, and no the number of
electrons per atom. The different nlodels give x values ranging from -0.227
XlO-'j to -0.115X10-6 e.m.u./g for respectively 1 and 5 free electrons. The
former value, which is closest to that observed, was obtained on the assunlption
that Au+ and Sn2+ions are associated with the lattice sites, a pair of localized
electroils are used in chemical bonding, and there is one conduction electron
per molecular AuSn unit.
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We have not beell able to account for the relnarkable increase of dia-
magnetism, particularly a t low temperatures, when vacancies are introduced
on the gold atom sites as the coinposition becomes richer in Sn.
I t has previously been reported (Beck et al. 1963) that strong oscillations
in the magnetic susceptibility of single crystals of AuSn are obtained as a
functioil of magnetic field a t 4.2' I< and lower temperatures. These oscilla-
tions will be the subject of a further study in attempting to obtain the Fermi
surface from the extrelnal cross-sectional areas which they establish. This
work is proceeding.

DISCUSSION
As no considerations would lead us to expect a filled valence band for AuSn
a t the absolute zero, the observed metallic coilductivity is in accord with alI
expectations. An open question is, however, how Inany coilductioll electrons
we may expect. There are several possibilities besides the five electrons per
formula unit AuSil arising from the normal valences of gold and tin. If tin
maintains two of its outer electroils in nonbondiilg orbitals, three conduction
electrons per AuSn unit are expected. There is also a remote possibility that
gold, as in the semiconductor CsAu, may form a closed Gs2 subshell, thus
leaving only one conductioil electroil per AuSn unit. Alternatively, the valence
of gold may be increased above unity if d states participate in the bonding.
The observed magnetic susceptibility sholvs that there are no d electrons
with unpaired spins, and calculations based on a simple model with the
magnetic susceptibility and Hall coefficieilt data favor a small, rather than a
large, number of conduction electrons per fornlula unit. Attempts to draw
detailed conclusions from the transport properties are unprofitable, but the
 JAN ET AL.: PROPERTIES O F AuSn 2265

absolute thermoelectric power definitely points to dominant electron rather

than hole co~~ductivity.Jan and Pearson (1963) have indicated a simple model
of Fernli surface, which would be consistent with observed anisotropies of
phonon drag thermoelectricity and electrical conductivity. The main features
of such a model could be most easily obtained with less than one conduction
electron per AuSn molecule, but the observation of several small pieces of
Can. J. Phys. Downloaded from www.nrcresearchpress.com by Depository Services Program on 11/12/14

Fermi surfaces in de Haas - van Alphen measurements indicates a more com-

plex situation. Nevertheless, present evidence leads us to suspect that there
are fewer conduction electrons in AuSn than the five per formula expected
fro111 normal chemical valences, and using this information we are proceediilg
with an interpretation of the Fermi surface from the results of de Haas -van
Alphen and nlagnetoresistivity measurements.

ACKNOWLEDGMENTS
We are very grateful to Drs. R. D. Ileyding and S. L. Bennett for some
of the magnetic susceptibility measurements.shown in Fig. 6 ; to Mr. J. W.
Fisher for preparing the alloys; and to Mr. A. Beck for growing, cutting, and
orienting the single crystals. One of the authors (A. I<.) wishes to thank the
OECD Organization for a travel grant and the National Research Council of
Canada for its kind hospitality.
For personal use only.

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