J. Phys. Chem. Solids, 1973. Vol. 34, pp. 321-335. Pergamon Press.

Printed in Great Britain

NONMETALLIC CRYSTALS WITH H I G H T H E R M A L

CONDUCTIVITY

G. A. SLACK
General Electric Research and Development Center, Schenectady, N.Y. 12301, U.S.A.
(Received 13 January 1972; in revisedform 30 May 1972)

Abstract--Nonmetallic crystals transport heat primarily by phonons at room temperature and below.
There are only a few nonmetallic crystals which can be classed as high thermal conductivity solids,
in the sense of having a thermal conductivity of > 1 W/cmK at 300K. Thermal conductivity measure-
ments on natural and synthetic diamond, cubic BN, BP and AlN confirm that all of them are high
thermal conductivity solids. Studies have been made of the effect on the thermal conductivity of nitro-
gen impurities in diamond, and oxygen impurities in AlN. The nitrogen impurities scatter phonons
mostly from the strain field, the oxygen impurities scatter phonons mostly from the mass defects
caused by aluminum vacancies. Pure A1N as well as pure SiC, BeO, BP and BeS conduct heat almost
as well as does copper at room temperature, while pure natural and synthetic diamonds conduct heat
five times better than copper.
All of the nonmetallic solids that are known to possess high thermal conductivity have either the
diamond-like, boron carbide, or graphite crystal structure. There axe twelve different diamond-like
crystals, a few boron carbide-type crystals, and two graphite structure crystals that have high thermal
conductivity. Analyses of the rock-salt, fluorite, quartz, corundum and other structures show no can-
didates for this class. The four rules for finding crystals with high thermal conductivity are that the
crystal should have (1) low atomic mass, (2) strong bonding, (3) simple crystal structure, and (4) low
anharmonicity. The prime example of such a solid is diamond, which has the highest known thermal
conductivity at 300K.

1. INTRODUCTION A review of the published data shows that

IN 1911 Eucken [ 1] discovered that diamond
was a reasonably good conductor of heat at
room temperature. In 1914 Debye [2] showed
theoretically why diamond was a good heat
conductor. In 1951 Berman e t al.[3] showed
that diamonds at room temperature conduct
heat even better than copper or silver. Silver
has the highest thermal conductivity of any
metal at room temperature where its thermal
conductivity, K, is 4.3 W/cmK. For copper
the value is 4-0 W]cmK. In metals the heat is
carried primarily by electrons, while in non-
metals at room temperature it is carried pri-
marily by phonons. We are interested in those
nonmetallic crystals which, like diamond, have
at room temperature a phonon thermal con-
ductivity comparable to or exceeding that of
copper and silver. Those crystals for which
K at room temperature exceeds 1 W/cmK will
be considered to possess a high thermal
conductivity.
321
only a few crystals fall into this category. Most
of them are adamantine (diamond-like) com-
pounds such as diamond [2-7], silicon carbide
[7], silicon[7,8] beryllium oxide[9], and
gallium phosphide[10-13]. The K at 300K
decreases in this series from 20 W/cmK for
diamond to 1 W/cmK for gallium phosphide.
In all of these crystals the atoms possess
tetrahedral coordination. Let us consider
what other crystals with the adamantine
structure[14] should have a high thermal
conductivity. The binary compounds A1N,
AlP, BAs, cubic BN, BP, BeS, and G a N
may all have K at 300K of greater than
I W/cmK. Possible ternary compounds [14-16]
with this structure are A12CO, BeSiN2 and
MgSiN2. However, from the compilation given
by Spitzer[17] it is apparent that ternary
compounds have lower thermal conductivities
than the corresponding binary compounds of
the same average atomic mass. Thus the r
322 G.A. SLACK

studies in the present work are limited to the 1900K for cubic BN. Thus we expect the
binary adamantine compounds. highest K values at 300K for the adamantine
Another structure with high thermal con- crystals.
ductivity is the a-boron structure [ 18]. Crystals The value of K from equation (1) is strictly
of B~2As2 have a K value of 1.2W/cmK at valid only for face-centered-cubic crystals
room temperature, while a-boron itself is having N = 1 atom per primitive crystallo-
predicted [ 18] to have a K of about 2 W/cmK. graphic unit cell. This means that the phonon
Samples of both graphite and hexagonal boron dispersion curves have only acoustic branches.
nitride are known [ 19, 20] to have high thermal For N/> 2 there will always be three or more
conductivity for heat flow perpendicular to the optic phonon branches. As a general rule
c-axis, i.e. along the tightly-bound sheets. these optic branches have very small group
Graphite[19] has K values up to 20W/cmK velocities, and hence contribute very little
while the highest value for hexagonal boron to K. This is particularly true for large N.
nitride [20] is about 2 W/cmK. For heat flow This means that crystals with large values of
parallel to the c-axis the K is considerably less. N have very low values of K. This type of
behavior was recognized by Eucken and Kuhn
2. PARAMETERS AFFECTING THE MAGNITUDE [33] in 1928. Reviews have been given by
OF K Missenard[34] and Spitzer[17], and recent
The recent theory of the magnitude of K work on this effect has been reported by
for nonmetallic crystals in the temperature Slack e t al. [18, 35]. Thus to find crystals with
range T I> 0, where 0 is the Debye tempera- high K we restrict the candidates to those
ture, has been given by Leibfried and structures with small values of N, the number
Schl6mann [21] and by Julian[22]. In this of atoms per primitive unit cell. Thus crystals
theory like SiO2 and A1203 are not expected to have
high K at 300K. Indeed they do not [36].
K = Bi"V180S/T3, ~ (1) The four rules for finding a nonmetallic
crystal with a high K are:
where B = some constant,/~ = average mass (1) low atomic mass, (2) strong interatomic
of an atom in the crystal, 3s = average volume bonding, (3) simple crystal structure, and
occupied by one atom of the crystal, and y = (4) low anharmonicity. Conditions (1) and
Griineisen's constant. The factor /~03 is (2) mean a high 0, condition (3) means low N,
maximized for light mass, strongly bonded and condition (4) means small 7.
crystals like diamond because the 03 term
dominates the behavior. The 3,2term is smallest
for adamantine crystals like Ge, Si and 3. ADAMANTINE COMPOUNDS STUDIED
diamond. The high temperature values of 3, In order to test the assumption that the
are 0.73, 0.45 and 1-3 for these three crystals adamantine compounds in general have high
respectively [23-26]. No other crystal struc- K values, measurements of K were made on
tures consistently have such small values the following crystals: Diamond, cubic BN,
of y. The alkali halides LiH, LiF and NaF, BP, AIN and BeO. The BeO results have
for example, have high temperature 3" values recently been published [9]. The other samples
of 1.4, 1.6 and 1-5, respectively [27-29]. Most of adamantine compounds studied are listed
crystals have 1 ~<3" ~< 2, while the soft rare gas in Tables l(a) and l(b). Both single crystal
crystals like argon[30] have 3"= 2.7. The and polycrystalline ceramic samples were
adamantine structure also possesses the used. The samples were generally in the
highest Debye temperatures known. These shape of rods with a rectangular, nearly-square,
are[31,32] 0=2240K for diamond and cross-section. The length of the rod is l and the
 N O N M E T A L L I C CRYSTALS 323

Table 1(a). Some adamantine samples for thermal conductivity studies

Size, mm Type Impurities
Sample Run No. I d [a] Source Color [e]

Diamond R201 5.0 3'8 SSC G E (b) Colorless 1'5 x 10~a/cm3-N

Diamond R207 4.9 1-1 SSC G E (b) Colorless 9 10JS/cm3-N
Diamond R208 5.1 1-1 NSC Light yellow 3.5 x 102/cma-N
bands
Cubic BN R189 7.7 2.5 HP G E (c) Grey ceramic 1% binder
Cubic BN R190 5-7 2.6 HP G E (c) Grey ceramic ~< 2 x 10~91cm3-O,C
BP R 151 1.8 1.0 SSC G E (d) Light grey,
transparent

[a]SSC = synthetic single crystal

NSC = natural single crystal
HP = hot pressed polycrystalline ceramic
[b]Grown by H. M. Strong and R. H. Wentorf Jr. of this laboratory, see Ref. [37]. Sample R207 was
a [ 100] axis rod.
[c]Prepared by H. P. Bovenkerk, General Electric Speciality Materials Dept., Worthington, Ohio.
The particle size was about 2 x 10-acm and the sample density was 97 per cent of theoretical. Sample
R 189 contained an oxide binder, sample R 190 contained no binder.
[d]Grown by F. H . Horn of this laboratory, see Ref.[18].
[e]The nitrogen in the SSC diamonds all occurs as dispersed nitrogen. The nitrogen in the NSC, R208
diamond occurs as platelet nitrogen, the dispersed nitrogen content is < 2 x 10tr/cm"~.The impurity content
of the BP is unknown, see Ref. [ 18] for comments.

Table 1(b). A IN samples for thermal conductivity studies

Size, mm Type c0[f] Totaloxygen[g] Kat300K
Run# / d [a] Source Color 10-Scm 10~atoms/cc W/cmK

R162 8.0 1.5 SSC Pechiney[b] Blue-grey 4.9809 3-----2 2-0

R 169 6.3 1"2 SSC Pechiney [b] 4.9806 3-- 2 2.0
R163 11-8 3.0 HP G.E. [c] Blue-grey 4.9789 11 -----2 0-28
R 174 11 "5 5.0 HP G.E. [c] Light-grey 4-9796 11 --- 2 0.65
R191 11"8 3.2 CPS NIRIM[d] Chalkwhite 4.9810 ~< 12 0.145
R196 9.5 2-3 HP G.E. [c] Steel grey 4.9788 43 +__2 0.41
R211 21"0 3-5 HP Cerac[e] Grey 4.9780 22-1 0-60
R212 12-7 3"3 HP G.E.[c] Chalk grey 4.9801 47---4 0.44
R213 11-0 2.7 HP G.E. [c] Grey 4.9793 11 1 0.74

[a]SSC = synthetic single crystal

HP = hot pressed polycrystalline ceramic
CPS = cold pressed and sintered ceramic
[b]Grown by sublimation at about 2100C in a commercial production furnace. Obtained from the
Pechiney Compagnie de Produits Chimiques et Electromrtallurgiques, Grenoble France with the
help of Dr. E. C. Lightowlers, University of London, see U.S. Patent 2,962,359 (1960). The crystals
were transparent with a blue-grey cast and had several brown streaks running through them. For
sample R 162 the crystallographic c-axis was tilted 62 away from the axis of the rod.
[c]Hot pressed in this laboratory at 1900"C and 300 atmospheres. The density was greater than
97 per cent of the theoretical density of 3.26 gm/cm a.
[d]Obtained from Dr. M. Iwata, National Institute for Researches in Inorganic Materials, Tokyo,
Japan. The sample had been cold pressed and sintered, the density was 62 per cent of theoretical.
[e]Obtalned from Cerac Hot-Pressing Inc., Menomonee Falls, Wis. The density was 94 per cent
of theoretical.
[f]Generally accurate to 5 x 10-12 cm.
[g]Measured using neutron activation techniques by Gulf Energy and Environmental Systems,
San Diego, California.
324 G.A. SLACK

diameter, d, is the diameter of a circle of repeated with 0.0025 cm dia. wire because
equal cross-sectional area. the only available crystal was quite small.
The synthetic diamonds were grown as The K values are believed to be accurate to
large, single crystals[37] in a high tempera- ___5 per cent except for BP, where the accuracy
ture, high pressure apparatus. The cubic is probably ___10 per cent.
BN [38] was synthesized in a similar apparatus.
The BP was grown from liquid palladium [18]. 5. RESULTS
The value of K is sensitive to the impurity (a) D i a m o n d
content of the samples, particularly those The K vs temperature curve for diamond is
impurities that enter as substitutional atoms given in Fig. 1. The K for the two synthetic
in the lattice. For diamond the commonly diamonds is shown to be larger than the best
troublesome impurity is nitrogen[6]. The
nitrogen content in samples R201, R207 and I I I I I
R201..-,~,:~
R208 was determined by measuring the opti- 0,AMON0
cal absorption coefficient at 480 or 1130 cm -1. 102 - R20 , --
In the synthetic crystals this occurs as dis-
persed nitrogen, in the natural crystals it
occurs mostly as 'platelet' nitrogen[39]. A
study of R208 by electron paramagnetic ~ IO -
resonance [40] placed the content of dispersed R 208
nitrogen in this natural crystal at < 2 x 1016/
cmz. In either case, platelet, or dispersed, the
nitrogen reduces the K of diamond.
In aluminum nitride, AIN, the common ~ I0C

troublesome impurities are carbon, oxygen,

and silicon. Mixed crystals of A1N can be
made with A14C3141, 42], A12Os[43], AI2OC
[44, 45], SiC [46] and probably SisN4. At low
concentrations the wurtzite crystal structure /
of AIN is retained. For the samples of AIN
in Table 1 the dominant impurity was oxygen. /
Apparently[43] the oxygen content in the I I I I I
10-2 3 IO 30 I00 300 I000
absence of carbon can be as large as 1.5 1022 TEMPERATURE, K
atoms/cm z. The oxygen content of the samples Fig. ]. T h e thermal conductivity o f two synthetic and one
was analyzed by neutron activation analysis natural diamond vs temperature. Two of Berman's curves
[47]. for types Ila and 1 natural diamonds are shown.
An upper bound is given to the impurities
in the BN. No information about impurities natural crystal of a Type IIa diamond
in the BP is available, see however Ref. [ 18]. measured by Berman et al. [5]. The maximum
K for R201 was Kmax= 175 W/cmK at 65K.
4. EXPERIMENTAL TECHNIQUE Sample R207 had a maximum of K = 140
The thermal conductivity was measured W/cmK at 70K. In Table 2 values are given
with an apparatus [48] described previously. for what is believed to be the intrinsic thermal
For all of the samples the temperatures were conductivity of diamond from 100 to 300K
measured with gold-cobalt versus manganin based on sample R201.
thermocouples of 0.0076cmdia. wire. For The natural crystal R208 was chosen to
the BP sample the measurements were have as large a concentration of nitrogen as
 N O N M E T A L L I C CRYSTALS 325

Table 2. The intrinsic thermal conductivity of found by Eucken [ 1] for diamond is probably
pure diamond, BP, SiC and LiH in error. He did not have his thermometers
attached directly to the diamond, and was
Thermal conductivity troubled by thermal contact resistance.
Temp. Diamond BP SiC LiH
The platelet nitrogen in natural diamonds
50 52 3-6 was shown by Kaiser and Bond[49] to be
70 43 1"75 nitrogen atoms substitutionally incorporated
100 130 > 14 28 0-93
150 65 10.0 15 0.46
for carbon. The nitrogen atoms do not pre-
200 40 6-5 9-5 0-29 cipitate as large (i.e. > 100 ~ dia.) size, second
250 27 4.6 6.5 0-20 phase inclusions. If they did, their effect on
300 20 3'5 4.9 0.147
500 8.0 [a] 2-2 0.067 K would be very small, contrary to the results
700 4.5 [a] 1.30 0.041 in Fig. 4.
1000 2.5 [a] 0.76 0.027 [b] The observations that the synthetic dia-
1300 0.50
1700 0.33 monds, because of their low nitrogen content,
have as high or higher thermal conductivity
[a]Estimated value. than the best natural samples makes them
[b]Extrapolated to melting point of 961 K. attractive for heat-sinking [52-56] semi-
conductor devices. A nitrogen content of
could be found in a good crystal, which was 1019/cm3, see Table 1A, decreases the K at
3.5 10~/cm3. Natural diamonds with con- 300K to about 18 W/cmK from a value of 20
centrations up to 4.2 102/cm3 have been W/cm K for pure diamond. This effect in syn-
reported[49, 50]. Crystal R208 has a maxi- thetic diamonds would be small for most
mum of K = 19 W/cmK at 85K and K = 6-8 practical applications.
W/cmK at 300K. The K vs T curve for this
sample with 3.5 102atom/cm3 of nitrogen (b) Boron nitride
is slightly lower than Berman's[5] sample No crystals of synthetic [38], cubic BN were
with 1-7 102atom/cm3 of nitrogen. The available that were large enough to measure
higher nitrogen content produces a lower K. Hence the measurements were made on
K. If the added thermal resistivity, AW, at polycrystalline ceramic compacts that had
300K produced by the nitrogen is proportional been made at high temperatures and pressures.
to the nitrogen concentration, An, then one The samples had a density of 97 per cent of
obtains theoretical, and a grain size of 2 x 10-3 cm. The
results are shown in Fig. 2. The K of R190, a
(AW/An) = 0.31 10-21 cm4K/W self-bonded compact, is higher that that of
R189 which contains some oxide binder
for the factor of proportionality. If one cal- between the grains. The K of R190 at 300K
culates W(no/An)_, where no is the number of is 1.8 W/cm deg. Hence it is concluded that
carbon atoms per unit volume in diamond, pure, single crystal cubic BN will have K > 2
i.e. no = 8-3, then W/cmk at 300K. How much greater is un-
certain, but the considerations in Section 7
AW(no/An) = 55 cmK/W (2) put this value at about 13 W/cmK. Thus one
might expect to see a considerable increase
If 4.2 10Z/cm3 is the maximum nitrogen in the K of cubic BN compacts as the bonding
concentration in diamond, then K I> 5-5 W/cm between the grains improves and the oxygen
K at 300K for any diamond. The result is in and carbon content within the grains decreases.
agreement with the results of Schorr [51]. The estimated K of BN derived from K
This means that the low K value of 1.7 W/cmK measurements on gas-solid mixtures by
326 G.A. SLACK

102
ioo
CUBIC BN

RI9
10I
IO"l
_>

z i-
8
>

w
~ 10o

io-2

u.I
-r
~- 10-1

I [ I I I
10-3 3 I0 30 I00 300 IO00
TEMPERATURE, K

Fig. 2. The thermal conductivity of polycrystalline cubic 10-2

BN vs temperature. The curve of Lezhenin et al. is an I 3 IO 30 I00 300 I000
estimate. TEMPERATURE, K

Fig. 3. The thermal conductivity for single crystals of a

Lezhenin et al.[57] is also shown in Fig. 2.
T h e true K of pure, cubic BN is probably much
higher.
(c) Boron phosphide
The K vs T curve for a single crystal of BP
is shown in Fig. 3. This sample has a maxi-
mum of r = 1 4 W / c m K at 80K. The results
from 50 to 300K indicate that the K of BP is
very close to that of BeO [9] in this tempera-
ture range. T h e intrinsic r values based on
these data are given in Table 2. T h e r vs T
curve in Fig. 3 is representative of a crystal
with probably less than 1019/cm 3 of impurities.
H o w e v e r , very little is known about the
possible impurities in these samples. T h e
results of Post[58] on BP ceramics from 475
to 865K show K values a factor of 6 lower than
would be expected, presumably due to impuri-
ties in his material.
(d) Silicon carbide
T h e thermal conductivity of moderately
pure SiC single crystals has been measured
number of adamantine compounds vs temperature.
[7] from 3 to 300K. At that time an attempt
was made to extrapolate these results to T =
0. Since then more data [59-61] have b e c o m e
available, and the previous extrapolated values
appear to be too large. Based on all the avail-
able information, the best current estimates of
the K of pure SiC are given in Table 2. T h e K
of SiC at T = 0 = 1080K is now believed to
be 0 . 6 7 W / c m K . This new extrapolation is
also shown in Fig. 3. In this extrapolation K
varies as T -1'5s for the range 200K ~< T ~<
1700K. This curve thus resembles the results
for BeO [9] for T > 200K, also shown in Fig. 3.
(e) Aluminum nitride
T h e present K results for AIN are shown
in Fig. 4 together with published data from
the literature [44, 62-64]. T h e literature results
for A1N, all for T 1> 300K, show considerable
variability, somewhat similar to the literature
results [7] for Si and SiC. T h e major factor
in producing this scatter in Fig. 4 appears to
 N O N M E T A L L I C CRYSTALS 327

I01 , i \ , i , 7B and the results in Fig. 4. Oxygen is the most

AtN \~PPERLIMIT common impurity in the samples studied [44,
62], but carbon was also a problem [44, 63].
R I 6 Z ~ \
~/~,~ \ TAYLO8R (i) Oxygen impurities. For the samples listed
~ 10o
CRYSTALS- ~
,,o, R174 \\ LENIE/ in Table l(b) the dominant impurity was
RI96 \ oxygen. Some care had been taken to eliminate
carbon, silicon, iron and other impurities. The
~ 10-1
oxygen enters the AIN lattice and substitutes
for the nitrogen up to very high oxygen
.ff concentrations [43]. In-this process one mole-
ANDREEVA
CE /o/ et ol.
~/ oL ONG8 cule of A10.670 substitutes for one molecule of
io-~
FOSTER A1N. Since the tetrahedral covalent radius of
oxygen is less than that of nitrogen[65], and
since metal vacancies occur on the aluminum
sites, the AIN lattice parameter should
io- I
Io t~o 36o ,oGo ,o,ooo decrease as the oxygen content increases.
TEMPERATURE, K This has been verified experimentally in
Fig. 4. The thermal conductivity of both single crystal Fig. 5 where the c-axis lattice parameter
(R162 and R169) and ceramic samples (others) of AIN determined from X-ray powder patterns has
vs temperature. The upper limit curve for pure AIN is been plotted vs the oxygen content deter-
an estimate based on the results shown in Fig. 3.
mined from neutron activation. All of the
points plotted in Fig. 5 were taken on samples
be the variable chemical purity and density that had been equilibrated at about 2000C in
of the AIN samples. an inert atmosphere or vacuum. Sample R196
The density of some of the samples studied is known to have a small amount of some
[62, 64] was only about 65 per cent of theore- second phase in it from the X-ray results. This
tical, and can account for low K values. See phase contains oxygen, but has not yet been
also the comments on sample R191 in Table identified [66]. From Fig. 5 it appears that the

4.98]
=-b~4.98C ~ R 174 MN
R2~St-~ ' I
Z
"~~?1.~1 RI96
~ 4.975
m
x

i I i I I I i I
4.97C
I0 20 30 40
OXYGENCONCENTRATION,102ocm-3

Fig. 5. The c-axis lattice parameter of AIN as a function of the oxygen concentration. Sample
R196 has two phases in it.
328
maximum solid-solubility of oxygen at about
2000C is 2 x 1021/cms. For some AIN + Al2Os
samples made in this laboratory at 100(2 the
smallest c-axis lattice constant found was
4.9685 .A, which corresponds to about 6 x 1021/
cm s of oxygen. This concentration is 1/3 of
the maximum reported previously [43] of 1.5
102~/cms. This lattice constant is similar to that
found by Kohn et al.[67] for AIN crystals
grown in the presence of air, see Table 3. The
Table 3. Lattice parameter of A I N
Lattice parameter, 10 -s cm
Co ao
4.991 3" 119
4.975 __.0.008 3" 110 ___0.005
4.965__+0.01 3-100.01
4.978 3" 111
4.980 3.111
4.982___0.003 3.1110.003
4.9816 0.0005 3" 1127 0.0003
/a/Calculated density is 3.255 g/cm a.
range of lattice parameters found [41,44, 67-
70] for A1N is given in Table 3. The very high
value found by Ott[68] is probably caused
by about 10 mole% of AI2OC in his crystals,
since they were made in a carbonaceous
atmosphere. Taylor and Lenie also found
[44] an increase in lattice parameter when
A12OC was incorporated. These results are
understandable since the lattice parameters
[45] of A12OC are about 2 per cent larger
than those of A1N. The other samples shown
in Table 3 have lattice parameters less than
Co = 4.9816 A a0 = 3.1127 ,~, (co/ao = 1.6004).
This is caused by the incorporation of Alo.670
into the lattice. The crystals studied by Kohn
et al. [67] were the most heavily contaminated.
The results in Fig. 5 show that
AC/Co = - 0"021 (An~no)
where no number of nitrogen atoms per cm s
= oxygen occurs in a second phase. The long
in pure AIN = 4.79 x 1022/cma, An = the
number of nitrogen atoms that have been
G.A. SLACK
replaced by oxygen, Co= c-axis lattice para-
meter of pure A1N, Ac = change in c-axis
lattice parameter caused by An. A study of
the co[ao ratio of various A1N samples doped
with Al0.oTO shows that this ratio remains
essentially constant at co/ao = 1.6004. Thus
the introduction of Alo.070 produces a volume
contraction of the A1N, and at 100% Al0.nTO
the volume would be 6.3 per cent less than that
of A1N. This crystal structure would have
Author Year Ref.
Ott 1924 68
yon Stakelberg and Spiess 1933 41
Kohnetal. 1956 67
Jeffi'ey et al. 1956 69
T a y l o r and Lenie 1960 44
Drum 1965 70
Present work [a] 1971 --
tetrahedral AI-O bonds 1.86/~ long, which
would be somewhat larger than the value of
1.82 ,~ found [71] in the tetrahedral structure
A1404C. Hence the hypothetical wurtzite
structure for A10.670 is only stable at lower
oxygen concentration where it forms mixed
crystals with AIN.
(ii) Thermal conductivity. Now that the
oxygen solubility in AIN is established, we
can begin to understand the K results in Fig. 4.
Let us consider K at 300K. Since K decreases
with increasing impurity concentration, the
thermal resistivity, W = K-I, is a more useful
quantity. In Fig. 6 a plot of W vs oxygen con-
centration is shown for several AIN samples.
Samples R169, R213, R174 and R211 are all
single phase ceramics, and the oxygen is in
solid solution in the AIN, as shown in Fig. 5.
(3) In samples R212, R196 and R163 the oxygen
content is too large for the A1N and some
horizontal bars for these three samples in Fig.
6 extend from the oxygen concentration in

, i , i
' ' I RI63
3
:
E
IRI96
qR212
/
Q:
R215
RI69
OXY(~r.N CONCENTRATION, 1020cm "3
Fig. 6. The thermal conductivity at 300K of AIN samples
as a function of the oxygen concentration. The heavy,
solid line extrapolates to r = 3'2 W/cmK for pure AIN.
the AIN, as determined from the A1N lattice
parameter in Table l(b), up to the total oxygen
content in both phases, as determined by the
neutron activation. The results in Fig. 6 can
be fitted by the heavy solid line which starts
at pure AIN where W0 = (1/3.2) cmK/W, see
Section 7. The incremental thermal resis-
tivity caused by the oxygen is AW = W-- W0.
The slope of the line in Fig. 6 is:
(AW/An) = 0.90 x 10-21 cm4K/W.
Then if no is the number of nitrogen atoms
per cm 3 in AIN, the results for Alo.erO in
A1N is:
(AWno/An) = 43 cmK/W.
This is quite similar to the value found in
equation (2) for nitrogen in diamonds.
So the thermal resistivity produced by
A10.670 impurities in AIN can explain the large
range of K values in Fig. 7. The magnitude of
the effect will be shown in Section 6 to be
about right. The reason that the K of tklN at
300K can sometimes be so low is that the
starting powder from which the sample is made
can contain up to 1.5 x 1022/cms of oxygen. In
most of the other adamantine compounds this
N O N M E T A L L I C CRYSTALS 329
I I I I I I
300K
A/N
3001(
6
4 BP&~BeO
I
0.~ t I I I I I
2 4 6 8 10 20 30
M~ 03/100, ~ cmK3
Fig. 7. The thermal conductivity at 300K of various
adamantine compounds vs the scaling parameter. The
arrows on the experimental points for AIN and cubic
BN indicates that the expected values for pure single
crystals lie on the line directly above. See Table 5.
impurity limit for commonly occurring
impurities is -- 5 x 102/cma.
6. ANALYSIS OF RESULTS
It would be very tedious to generate
computer fitted K VS T curves for all of the
samples in Figs. 1-4. Hence a simpler
approach will be taken. A computer fit for
silicon and for a diamond sample similar to
(4) R208 in Fig. 1 has been carded out by
Agrawal and Verma[72], and they conclude
that the point impurity scattering in diamond is
much higher than predicted by the carbon iso-
topes. It is clear, now, that nitrogen impurities
are responsible. At temperatures below 4K the
Kof diamond is well explained [72] by boundary
scattering. Similarly in Fig. 3 the K at 2K of all
of the samples except the BP (R151) is
explained by boundary scattering. Some
impurity scattering probably exists in the BP
sample for T < 100K. The Kat room tempera-
ture (and above) of the pure crystals will
330 G.A.
be treated comprehensively in Section 7. The
main feature of present concern is the
explanation of the magnitude of the impurity
effect on K.
Impurity effects are important in AIN and
diamond, see equations (2) and (4). The effect
of substitutional impurities on the K of
adamantine compounds has been treated by
Abeles[73] for the temperature range T~>
0. He considers that a substitutional impurity
produces both a local mass difference, AM,
and a local lattice mismatch, Aa, in the lattice.
In his treatment he considers the parameter
gamma:
= x,xI4 + 40 (5)
where x is the fraction of lattice sites occupied
by the impurity, and the subscript A means
Abeles. The quantity Fa is 12 times larger
than the customary[48, 74] definition of F.
Hence:
r = (FA/12) (6)
For substitutional A1o.670 impurities in AIN
one molecule of Alo.670 is assumed to produce
a small mass change in the nitrogen lattice,
i.e. 16 vs 14, and a larger mass change in the
AI lattice by creating 1/3 of a vacant lattice
site. The method of calculating F when two
sublattices are involved has been outlined
previously[74]. Thus for one molecule of
Al0.s70 in AIN:
-~-M)2 = 0.289 + 0-005, (7)
where the first term on the right is for the AI
lattice and the second is for the nitrogen
lattice. The (AS/a) term in equation (5) is
2.1 x 10-z from equation (3). The result is:
FA = 0"310x(1--x). (8)
If a reasonable value of a = 2.5 is assumed
for a in equation (25) of Abeles [73], then for
SLACK
A1N:
W = 238 I" A cmK/W. (9)
For low concentrations of A10.670:
x(1--x) = x = An/no.
Thus the calculated value is
(AWno/An) = 74 cmK/W (10)
for the temperature range T/> 0. The experi-
mental value at T = 0.32 0 is given in equation
(4). The agreement is good considering the
assumptions involved. Thus the major source
of the phonon scattering in AIN produced by
A10.670 impurity is the mass difference of the
A1 vacancies.
For nitrogen in diamond Agrawal and
Verma[72] have shown that if the point
impurity scattering relaxation time, %, is
given by
tp-a = Ao9 4,
where ~o is the phonon frequency in rad/sec,
then
A = 2.09 x 10-4's sec 3
for Berman's sample with 1-7x 102/cm3 of
nitrogen. This value of A corresponds [73] to
Fa = 3"65 x 103.
Since the mass difference between carbon and
nitrogen is small, the calculated value of l'a
from equation (5) assuming A6 = 0 is
Fa = 2"8 10-s
or too small by a factor of 140. Clearly Aa > 0
for nitrogen in diamond, and most of the
phonon scattering produced by the nitrogen
is caused by the strain field of the lattice
mismatch and not by the mass difference.
Equation (5) would require:
(Aala) = 0.3
 NONMETALLIC CRYSTALS 331

to account for the observed effect of nitrogen.
This value of A8 appears to be too large from
the work of Kaiser and Bond [49] who find:
(A8/8) = 0.053.
So the situation for nitrogen in diamond is
not clear, but the phonon scattering cross-
section is clearly larger than that due solely
to the mass difference between nitrogen and
carbon.
7. SCALING P A R A M E T E R S FOR K AT 300K
From the present measurements on
diamond, cubic BN, BP, and A1N it is clear
that the pure crystals all qualify as high K
solids. F r o m equation (1) we take the expres-
sion A~803 as a convenient scaling parameter
for the adamantine compounds at a fixed T
of 300K. The Grfineisen parameter 7 has
been omitted, since it is not known for all of
the crystals. In Table 4 this scaling parameter
has been calculated for all of the adamantine
crystals that have high K. T h e literature Ref.
[7, 9, 3 1 , 3 2 , 75-80] for 0 and K are also given
in Table 4. T h e 0 for SiC was computed
from estimated elastic constants [76, 77].
The 0 for BeS was estimated from a com-
parison[78, 79] with BeO. The 0 for A1N was
calculated from the measured heat capacity
[81] and a guess as to the probable extra-
polation of the 0 vs T curve to absolute zero.
The 0 for G a N was calculated using the
approach of Steigmeier[32] and the known
0 values of BeO and AIN. In Fig. 7 K has been
plotted versus this scaling parameter. The
agreement is good except for A1N and BN
where the observed K falls much below the
line. F o r these crystals the r is probably
limited by impurities, and hence is lower
than the intrinsic K. In fact the extrapolated
r for pure A1N at 300K from Fig. 6 is 3.2
w/cmK, in agreement with the expected value
from Fig. 7. F o r pure, cubic BN the expected
K at 300K from Fig. 7 is 13 W/cmK. F r o m
Table 4 and Fig. 7 it is possible to make
estimates of the K to be expected for the
crystals BeS, BAs, G a N and AlP for which
no data exist. T h e s e estimates are given in
Table 5 together with the known K values for
the other crystals. A table similar to Table
5 has been made by Steigmeier[82] for other
adamantine crystals where K < 1 W / c m K at
300K. F r o m Table 5 it is predicted that there
are twelve adamantine crystals that can be
classed as high K nonmetals. O f these dia-
mond has the highest K, and cubic BN is a
close second. Measurements on high purity
single crystals of several o f the others are
needed to confirm these predictions.

Table 4. The scaling parameter ffl~O3for adamantine compounds

with high thermal conductivity [a]
lffl 28 0 ff18031100 Reference
for
Crystal g 10-a cm K gcm Ka r 0
Diamond 12.01 3.56 2240 23"8 3-6, P 31
Silicon 28.09 5.43 645 2'05 8 75
BN(cubic) 12.41 3.62 1900 15"4 P 32
SiC 20-05 4.36 1080 5"5 7, 59-61 7, 76.77
BeS 20-54 4.85 900 3"63 -- 78.79
BP 20.89 4"54 985 4"53 P 32
AlP 28.98 5.45 588 1-60 -- 32
BAs 42.87 4-78 625 2"50 -- 32
GaP 50.34 5-45 445 1"21 10-13 80
BeO 12-51 3.81 1280 5.00 9 9
AIN 20-49 4.37 950 3"84 P 81
GaN 41.86 4.49 600 2"03 -- 32

[a]P = present work, 28 = the lattice constant for the cubic crystals.
332 G.A. SLACK

8. LITHIUM HYDRIDE y = 1.4, for most of the adamantine compounds

The compound LiH has an average y ~-0.7. Hence we expect, from equation (1)
atomic mass M = 3.97 g, a Debye temperature the K of LiH to be lower by a factor of (1-4/
0 = 1070K as calculated from the elastic 0.7) z = 4. Thus even the rocksalt compound
constants[27], and a simple crystal structure with the l o w e s t / ~ and highest 0 is too anhar-
(NaC1 type) with N = 2. It has a value for monic, i.e. has too large a phonon-phonon
M603 of scattering, to classify as a high K crystal. In
Fig. 8 the K curves for LiF [90-92] and N a F
M803/100 = 0.993 g cm K 3. [93, 94] are shown for comparison with LiH.
At 300K and above the K of LiF is slightly
From Fig. 7 we might expect LiH to have lower and that of N a F is slightly higher than
K - 0.8W/cmK at 300K. Measurements of that of LiH. The scaling parameters [95-97]
K have been made[83-89] for LiH, and are are also similar. This means that the K of
shown in Fig. 8. See also Table 2. The experi- LiH behaves like the r of the alkali halides.
mental value of r is K = 0"15 W/cmK at 300K. A survey of the r of other rocksalt structure
This is lower than predicted by a factor of compounds indicates that none[33, 74, 98,
5-3. This difference between LiH and the 99] of them can be classed as a high K Crystal.
adamantine crystals can be attributed.mainly
to the difference in y. For LiH we have[27] 9. CONCLUSIONS
(1) High purity synthetic diamonds have K
values somewhat greater than the best
natural diamonds so far studied. The K of
103 diamond is sensitive to the nitrogen content,
and at 300K varies from 20 W/cmK in pure
diamond to about 5.5 W/cmK for the most
heavily doped crystals. The phonon scattering
is probably caused by the strain field around
the nitrogen impurities.
(2) The r of A1N is sensitive to the oxygen
content, and at 300K varies from about 3.2
W/cmK in pure AIN to about 0-5 W/cmK for
2 1021/cm3 of oxygen. Even lower K values
can occur at higher oxygen contents or in
two-phase ceramics. The phonon scattering
in the oxygen doped samples appears to be
caused by the mass defect of the aluminum
ItV its0 I--
vacancies as A10.6~O is dissolved in the AIN.
(3) In order for a nonmetallic crystal to pos-
sess high thermal conductivity it must have
LiH
VETRANO low average atomic mass, strong interatomic
+ FIELDHOUSEet ol.
MAM~ING8 McKEE bonding, a simple crystal structure, and low
o THACHER
anharmonicity.
(4) There are twelve adamantine crystals
I I
DO
t
300
I
1000 with high thermal conductivity. This means r
TEMPERATURE,K values ~> 1 W/cmK at 300K. These range
Fig. 8. T h e thermal conductivity o f L i H , L i F and N a F from diamond to gallium phosphide, and are
vs temperature as reported in the literature. listed in Table 5. Their K values at 300K are
 N O N M E T A L L I C CRYSTALS 333

T a b l e 5. T h e r m a l c o n d u c t i v i t y at 3 0 0 K o f a d a m a n t i n e
c o m p o u n d s . T h e v a l u e s in p a r e n t h e s e s are e s t i m a t e s f r o m
Fig. 7

K K K
Crystal W/cmK Crystal W/cmK Crystal W/cmK
Diamond 20 BP 3.6 GaN (1"7)
BN(cubic) (13) A1N (3"2) Si 1.6
SiC 4-9 BeS (3"0) AlP (1"3)
BeO 3"7 BAs (2"1) GaP 1-0

proportional to the scaling parameter .~t~0a,
see equation (1).
(5) Several other crystals with the a-boron,
boron carbide, or graphite structures also
possess high K values.
(6) There are no crystals with the rocksalt
structure, not even LiH, that possess high
thermal conductivity. This is caused primarily
by lower 0 and higher T values in these
compounds compared to the adamantine
crystals.
Acknowledgements--I would like to thank J. H.
McTaggart and W. S. Knapp for their help in making
the thermal conductivity measurements. Thanks are also
extended to F. H. Horn for the BP crystal, H. M. Strong
for the diamonds, E. C. Lightowlers for the AIN crystals,
H. P. Bovenkerk for the ceramic, cubic BN samples,
J. A. Palm, J. W. Szymazek and M. P. Borom for the hot-
pressed AIN samples, and R. M. Chrenko for advice
about nitrogen impurities in diamonds. In addition, I
am grateful to J. P. Moore for sending me the data on
the thermal conductivity of LiF prior to publication, and
to P. D. Thacher for the data on LiH.
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