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The electrical conductivity of single-crystal alumina

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1964 Br. J. Appl. Phys. 15 633

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BRIT. J. AWL. PHYS., 1964, VOL. 15

The electrical conductivity of single-crystal

alumina
J. A. CHAMPION
Metallurgy Division, National Physical Laboratory, Teddington, Middlesex
MS. received 5th February 1964, in revised form 16th March 1964
Abstract. The electrical conductivity of alumina crystals with varying chromium
content has been measured in air by a two-tenninal d.c. method over the temperature
range 20-85O"c. When fist heated all specimens showed peaks and pulses in the
conduction current similar to those reported by Tucker and Gibbs for clear sapphire.
After several heating and cooling cycles the variation of conductivity with temperature
became reproducible with an activation energy averaging about 0.5 ev in the range
200-450"~and about 1.7 ev in the range 450-850"~. Conductivities at 850"c of
1 x lo-' ohm-' cm-l for clear sapphire and of 2 x 10-lo ohm-l cm-l for pi& ruby
are compatible with the values obtained by Harrop and Creamer, but their suggestion
that trace impurities of iron control the conductivity is not wholly substantiated.
1. Introduction
Interest in the growth and properties of single crystals of alumina doped with chromium
has increased since the advent of ruby masers and lasers. For such applications the
degree of purity and perfection of the ruby crystals is of paramount importance. Macro-
scopic inclusions and imperfections affect the optical absorption and transmission pro-
perties of laser crystals, and impurities and imperfections on the atomic scale can cause
broadening of the emission linewidth. Any impurities and imperfections that are present
in an insulator such as alumina are also likely to affect the electrical conductivity, so that
the measurement of this property may well prove to be a useful adjunct in the study of
laser crystals.
There have been several previous determinations of the variation of electrical conductivity
of single-crystal alumina with temperature (e.g. Rochow (19381, Wachtman and Maxwell
(1954,1957), Tucker and Gibbs (1958), Pappis and Kingery (1961) and Harrop and Creamer
(1963)). The majority of these determinations have been on undoped alumina samples and
at high temperatures where the conductivity is more easily measured and where repro-
ducible results are more readily obtained. Even so, values for the conductivity reported by
different investigators for reasonably pure specimens vary over several orders of magnitude
with experimental activation energies between 1 . 5 and 5.8 ev. This wide variation
indicates that the electrical conductivity of alumina is probabIy highly dependent on the
perfection and impurity content of the particular crystals examined.
It has been established that electronic semiconduction is the mechanism of conduction
in alumina at high temperature (Cohen 1959). In addition, Pappis and Kingery (1961)
have found p-type semiconduction in alumina at oxygen pressures above about 10-5 atm,
and n-type semiconduction at lower oxygen pressures. This behaviour they slscribe to
departures from stoichiometry.
Apart from Harrop and Creamer who investigated the conductivity of crystals both
undoped and doped with chromium, over the temperature range 800-1500~, there appear
to have been few previous measurements on ruby. Also, apart from the work of Tucker
and Gibbs, few measurements appear to have been made on alumina below 800'~.
In the work described in this paper single crystals of alumina with varying contents of
chromium and other impurities have been studied. Measurements of electrical conductivity
have been made over the comparatively low temperature range from room temperature up
to 8 5 0 " ~ . The crystals examined were grown by either the Verneuil or the fluxed-melt
techniques. The possible influence of impurities and imperfections on the results is
discussed.
633
 634 J. A. Champion
Analysis and orientation of crystal specimens
Specimen c2 P2 R2 FM2
Method of growth Vemeuil Vemeuil Vemeuil fluxed-melt
Angle between c axis 31" 11" 82" 90"
and current
Analysis (wt %) Cr n.d. 0.046 0.34 0.055
(<0.001)
Fe 0.000 5- 0.001 5- 0.001 5- 0.018
0.001 0 0.002 5 0.002 5
Pb n.d. n.d. n.d. 0.052
(<0.005) (<0.005) (<0.005)
Mg 0.000 5- 0.000 5- 0.000 5- 0.000 1-
0~0010 0~0010 0.001 0 0.0003
Si 0.000 2- 0.000 1- 0.000 1- 0.000 1-
0-0005 0.0002 0.0002 0.0002
Mn ad. ad. n.d. 0.000 5-
(<O.OOO 5 ) (<O.OOO 5 ) (<O.OOO 5 ) 0.001 0
cu n.d. n.d. n.d. n.d.
(<O.OOO 1) (<O.OOO 1) (<O*OOO 1) (<O.OOO 1)
Ni n.d. n.d. n.d. 0.000 5-
(<O.OOO 5 ) (<O*OOO 5 ) (<O.OOO 5 ) 0.001 0
MO n.d. n.d. n.d. n.d.
(<O.OOO 5 ) (<O.OOO 5 ) (<O.OOO 5 ) (<O.OOO 5 )
n.d. = not detected.
The following elements were not detected in any specimens (<0.001 0%): Bi, Sn, Ca, Be, v,
Zr, Pt, Pd, Cd, Ag, Au, CO,B.
The following elements were not detected in any specimens (<0.005%): Sb, As, Hg, Zn.

2. Experimental
Single crystals of clear sapphire and of ruby containing up to 0'34% chromium were
investigated. Some of the crystals had been grown by the Verneuil technique, mainly by
Salford Electrical Instruments. Others were grown in this laboratory out of solution in
lead fluoride by the fluxed-melt technique (White 1961). The crystals were analysed
chemically for chromium and iron and spectrographically for other metallic elements.
Fluxed-melt crystals were also analysed chemically for lead. The results are given in the
table; at the very low levels concerned the spectrographic figures are accurate relatively to
within &50% and absolutely to within a factor of 3. The accuracy of the chemical results
should be much greater ( 5 5 % ) . The orientations of the specimens were determined by
x-ray diffraction and are also given in the table.
The method of measurement of conductivity was similar to that used by Tucker and
Gibbs (1958). Specimens were cut in the form of rectangular bars approximately
3 mm x 3 mm X 20 mm from Verneuil bodes and approximately 1 mm x 2 mm X 10 mm
from tabular fluxed-melt crystals. Prior to mounting, each specimen was etched in ortho-
phosphoric acid at 350"c for a few minutes (Scheuplein and Gibbs 1960), washed in water
and its ends metallized by painting with Liquid Bright Platinum (Johnson, Matthey & Co.
Ltd.) and tiring in air at 600"c for 30 minutes. Platinum foil was wrapped round the ends
of the specimen and bound with platinum wires. The crystal was freely supported by
these wires in a horizontal tubular furnace. Two liners were inserted inside the furnace
tube. The outer liner was an earthed tube of magnetic stainless steel to shield the specimen
from electromagnetic pick-up and the inner liner was a silica tube to prevent contamination.
A potential of 100 v was applied across the specimen and the current flowing measured
with a vibrating reed electrometer with an input resistance variable between IO3 and 10''
ohm. Preliminary experiments showed that the current flowing through the specimenswas
a linear function of the applied voltage and independent of its sign. The output from the
electrometer was fed to a potentiometric pen recorder. The furnace and potential supply
were totally enclosed in earthed metal boxes and screened connecting cable was used
 The electrical conductivity of single-crystal alumina 635
throughout. With all the apparatus screened it was possible to measure conductances
down to Ohm-'.
Also connected to the recorder was a Pt-13% Rh/Pt thermocouple placed near the
specimen to measure the temperature. A similar thermocouple was connected to a pro-
gramme controller which reslated the furnace current.
The procedure usually adopted was to increase the temperature of the specimen from
2O"c to 8 5 0 " ~at a rate of 5 degc min-l, although a slower rate of 2 degc min-1 was some-
times used. The temperature was generally held constant at 850"c for 1-2 hours after
which the furnace was switched off and the specimen allowed to cool. The rate of cooling
was 10 degc min-I at 850"c, decreasing to 1 degc min-I at 200'~. Temperature and
conductivity were recorded throughout.

3. Results
During the initial heating the conductivity of each specimen followed a general pattern.
From room temperature up to about 1OO"c the conductivity fell, probably owing to the
evaporation of moisture, reducing surface conduction. As the temperature increased
further the general level of conductivity rose, but the conduction current showed at least
one peak before 850"~. All specimens showed a peak in the temperature range 530-56O"c
and transient pulses in the conduction current which started at about 440"c and continued
until the temperature reached about 600 or 650"c. Specimens C2, P2 and R2 also showed
smaller peaks, but no pulses, in the range 150-23O"c. The pulses were too rapid to be
resolved on the chart recorder and often appeared to have time constants and repetition
rates of less than a second. The amplitude of the pulses varied; typically they produced an
increase in current of about 10% but very occasionally the increase was nearer 100%.
During the steady period of 1-2 hours with the temperature at 850"c the conductivity
usually fell somewhat. On cooling the conductivity fell steadily.
During the second heating of the specimen the conductivity followed the previous cooling
curve fairly well. After three or four heating and cooling cycles the conductivity against
Temperature ('C)
700 500 400 300 250 200
lo I t I I 'I

1 0 ~(T1 in~ OK)

Figure 1. Variation of electrical conduct- Figure 2. Variation of electrical conduct-

ivity U with temperature for fluxed-melt
ruby specimen FM2, runs 1 and 2.
ivity U with temperature T for specimen
C 2 : O, run 3; * , run 4. The full line
represents the relationship:
0 = 8 x 10-2 e-1.76/kp + 5 x 10-1Oe-O*53/kT
ohm-km-l (k = 8.62 x ev degK-l).
 636 J. A. Champion
temperature curves became reproducible. NOpulses were observed after the initial heating,
n e above sequence was followed for all the Verneuil crystals with only minor variations
The flued-melt sample also behaved similarly except that the pulsation of the conduction
current was much less marked. As an example, the variation of conductivity with tern-
perature for the fluxed-melt specimen during the first two heating and cooling cycles is
shown in figure 1.
To illustrate the degree of reproducibility obtained after a few heating and cooling cycles,
figure 2 shows the results of runs 3 and 4 for specimen C2. Here the conductivity U has been
plotted on a logarithmic scale against the reciprocal of the absolute temperature. Actual
points have been plotted as taken from the recorder charts. The full line, which is quite a
good fit to the experimental points, was calculated from the equation

U =8 x exp +5 x 10-10 exp (-

where k , Boltzmann's constant, equals 8.62 X 10-5 ev degK-l.
The jinal reproducible results for all the four specimens are shown in figure 3 in which
the experimental points have been omitted for the sake of clarity. The results of Harrop
and Creamer (1963) and those of Rochow (1938) are also shown on this graph.

4. Discussion
The present results may be compared with those of Tucker and Gibbs (1958) for clear
sapphire rod. These authors observed similar peaks and pulses in the conduction current

Temerature ("C)

\\

Figure 3. Variation of electrical conductivity LJ with temperature T for various specimens of

sapphire and ruby: C2, P2, R2, FM2, present work; HC, HP, Harrop and Creamer (1963), clear
sapphire and pink ruby containing 0.020% Cr respectively; +, Rochow (1938), clear sapphire.
 The electrical conductivity of single-crystal alumina 637
during the initial heating period. They found a peak at 250'c with pulsing in the range
400-450"~after contamination with water; a peak at 350"c and pulsing in the range
375-415"~after contamination with 6N HC1; a peak at 705"c and pulsing in the range
725-750C after contamination with 6N NaCl; and a peak at 570"c and pulsing in the
range 670-715"~after contamination with 6N Mg(NO,),. In common with the present
work, they observed that the peaks and pulses were absent during subsequent heating cycles.
They also found that the peaks and pulses were absent if the specimen had not been con-
taminated and the experiment conducted in dry nitrogen. One point of difference is that
the pulses observed by Tucker and Gibbs always occurred after the peak had been reached,
whereas in the present work the peaks generally occurred in the pulsing region. The small
peaks observed in the present work in the range 150-230"~may be associated with removal
of adsorbed water (cf. the peak at 250"c observed by Tucker and Gibbs) and the larger
peaks in the region 530-560'~ may be connected with orthophosphoric acid treatment.
Tucker and Gibbs interpreted their results, which were supported by measurements on
crystals in which the dislocation content had been increased by plastic deformation,
in terms of adsorption of impurities along dislocation lines at low temperatures and their
subsequent expulsion at higher temperatures. According to the model of Tucker and
Gibbs the pulses could occur when an ionic impurity is suddenly 'drained' from a disloca-
tion system by thermal energy. The thermal asymmetry between the introduction and
removal of the impurities implies the existence of a potential barrier at the surface. If this
explanation is correct the extent of the pulsing and the temperature of its occurrence might
be expected to depend on the degree of perfection of the crystal lattice. This supposition
could account for the difference between samples observed in the present work. In parti-
cular, it could account for the fact that fewer pulses were observed with the fluxed-melt
crystal than with the Verneuil crystals since etch-pit studies have indicated that the
dislocation density is lower in fluxed-melt crystals by a factor of about 10. Thus the
present work appears to support the mechanism proposed by Tucker and Gibbs.
Since the final results are so reproducible it would seem that predominantly bulk con-
duction was being observed rather than surface conduction in adsorbed (moisture) fdms.
Below about 200 "c, however, where the conductivity was not so reproducible, and possibly
also during the initial heating period to 850"c, surface conduction may have been appre-
ciable.
The final reproducible results, shown in figure 3, indicate that the conduction process in
all four specimens can be represented, to a good approximation, by an equation of the
tvne

E, - 1.7 ev, E, N 0.5 ev, u1 N 10-?-10-1 ohm-l cm-l, u2 - 10-11-10-9 ohm-' cm-l.

The first term in the equation is dominant from 8 5 0 " ~down to about 4 5 0 " ~and the second
from about 450"c to 200"c.
There does seem to be a real difference between the final conductivities of the four
specimens since their range considerably exceeds the estimated experimental error (<10%).
The mechanism of conduction appears to be electronic rather than iorric since the measured
values of conductivity all very greatly exceed those calculated by Harrop and Creamer
(1963) from the Nernst-Einstein equation using diffusion data. The final results for
specimens C2, p2 and R2 indicate that the chromium content is not the major factor in-
fluencing the conductivity. The conductivities found for C2 and P2 are, however, com-
patible with the values found by Harrop and Creamer (1963) for clear sapphire and for
ruby containing 0.020 % chromium, and with the results of Rochow (1938) on clear sapphire.
Harrop and Creamer propose that the conductivity of the ruby is lower than that of the
sapphire because of its slightly lower iron content (<5 compared with <20 parts per
million). They give reasons for suggesting that iron impurity ions may change their
638 J. A. Champion
valence state but are unable to explain why the chromium ions although also multivalent do
not behave similarly.
me present work does not wholly support the contention of Harrop and Creamer
regarding the role of iron at such low impurity levels. Specimen P2 has a lower con-
ductivity than C2 but a higher iron content (15-25 as against 5-10 parts per million).
However, the appreciably higher iron or lead content of FM2 may be the reason for this
specimen having the highest conductivity.
Since corundum has a hexagonal structure one might expect the conductivity in the
direction of the c axis to differ from that perpendicular to it, and the measurements of
Geller et al. (1946) at about 1 2 0 0 " indicate
~ such a difference. The present results could be
explained on the hypothesis that the conductivity decreases with the addition of chromium
and increases as the c-axis-current angle approaches go", but an insufficient number of
samples has so far been studied for firm conclusions to be drawn.
The differences in the final conductivities of the four specimens may be due to some
interaction effect between the impurity ions or to inhomogeneity in the distribution of
impurities or to defects in the crystal lattice. Read (1954) has studied theoretically the
electrical effects of dislocations in the diamond-type lattice (with particular reference to
germanium). He has shown that dislocations should produce acceptor-type energy levels
in the forbidden gap. (An electron paired with a dangling bond probably has less energy
than a free electron in the conduction band yet more than an electron in the valence band.)
Although no similar study appears to have been made for the corundum lattice, presumably
by analogy dislocations can be expected to produce energy levels in the forbidden gap,
although precise position and effect can only be conjectured.
Further experiments aimed at correlating the electrical conductivity with other physical
properties are needed before the points raised in this discussion can be resolved. In
particular further study of the degree of crystal perfection, for example by x-ray techniques
might be helpful.
Additional experiments to see if there is any correlation between the laser performance
of ruby crystals and their electrical properties might also be worthwhile. A laser crystal
can only produce a simple set of sharp emission lines if the lattice sites occupied by the
active ions are all crystallographically equivalent. Departures from this ideal situation may
produce observable electrical effects as well as affecting the laser properties.

Acknowledgments
The author gratefully acknowledges the supply of synthetic sapphire and ruby from
Salford Electrical Instruments, Ltd., and the assistance of D. R. Oakley during the early
stages of the work.
The work described above has been carried out as part of the General Research Pro-
gramme of the National Physical Laboratory and this paper is published by permission of
the Director of the Laboratory.

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