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J. Phys. Chem. Solids.

Pergamon Press 1966. Vol. 27, pp. 1125-1131.

Printed in Great Britain.

ANOMALIES OF NICKEL

IN THE ELECTRICAL

CONDUCTIVITY

OXIDE ABOVE ROOM TEMPERATURE


M. W. VERNON and M. C. LOVBLL

Physics Department, Royal Military College of Science, Shrivenham, Swindon, Wilts


(Received 23 August 1965; in revisedform 10 December 1965)

Abstract-The electrical conductivity of various specimens of single crystal NiO has been measured in the temperature range 293K-67SK. The specimens from several sources, show two systematic changes of slope in the plot of log o vs. l/T, near 390K and 523K respectively. The anomaly at the higher temperature is linked only with the magnetic transition at the Nobelpoint. This anomaly is sometimes accompanied by thermal hysteresis effects which appear to be strain dependent. That near 390K shows no hysteresis and is ascribed to the small rhombohedral distortion from the face centred cubic rock salt structure. This distortion is explained as a small Jahn-Teller effect arising from the spin degeneracy of the Ni2+ ground state. INTRODUCTION has been shown in the electrical properties of nickel oxide because of its behaviour as a magnetic insulator and the apparently low mobility of the current carriers. Electrical conductivity measurements have been made by a number of workers both on sintered specimens of pure NiO and on lithium doped samples,(lp2) but comparatively few on pure single crystals. It is well known that a magnetic transition occurs at 523K associated with spin ordering from the antiferromagnetic to the paramagnetic state. This has been associated with the existence of a small crystallographic distortion from face centred cubic above, to a rhombohedral structure below the NCel point. In addition anomalies have been observed at this temperature in a number of physical properties including thermal expansion, Youngs modulus and electrical conductivity.(s) The effect on electrical conductivity can easily be masked by poor samples or the presence of significant amounts of impurity. A change in activation energy for conduction determined from plots of log cr vs. l/T at the NCel point in NiO has been observed to be positive,(l) negative@) and zero.@) The majority of results in good samples show a negative change, the others illustrating the influence of specimen preparation. In an attempt to overcome this variation of results, crystals have been grown in this laboratory. An Epitaxial method was used to grow almost stoichiometric, relatively strain free crystals and a floating zone method to grow much larger crystals which were less stoichiometric and more highly strained. The object of this work was to investigate the electrical conductivity of single crystals of NiO over a range of temperatures about the NCel point.

CONSIDERABLEinterest

EXPERIMENTAL

Materials
Crystals have been grown epitaxially (Specimen A) using a method similar to that of CECH and

ALESSANDRINI.@) Growth occurs from NiBr on to a MgO substrate at 640C in an atmosphere ofwater vapour. These crystals were about 200~ thick and were removed from the substrate by dissolving the latter in sulphuric acid held just below its boiling point. Small pieces measuring about 1 mm square were used for the electrical measurements. NiO crystals have also been grown by a floating zone method using a carbon arc image furnace.(v) These crystals were grown in air from spectrographically standardized NiO powder used in the form of sintered rods. The growth rate was about 1 cm/hr. (Specimen B).

1125

1126

M.

W.

VERNON

and

M.

C.

LOVELL

Some specimens have also been obtained other sources for comparison as follows:

from

1. The Fuji Titanium Industry Co. Ltd., Japan, grown by the Verneuil technique (Specimen C). 2. The Air Force Cambridge Research Laboratories, U.S.A. (Verneuil)* (Specimen D). 3. The Philips Research Laboratories, Eindhoven, grown by the floating zone method (Specimen E).* Samples from these crystals used in the electrical measurements were in all cases small parallelopipeds measuring a few millimetres, cleaved from the as grown crystals.
METHOD

latter point was further confirmed by subsequent spectrographic analysis. At least two samples of crystals from each source were measured and again consistent results were obtained. Some examples are given in Table 1. Measurements were made on the crystals as obtained and after annealing for 3 hr in air at 1000K. The fact that there are only very small differences in the measurements on the arc grown crystals before and after annealing is additional evidence that the heating during measurement does not change the chemical composition of the crystal.

RJ3SULTSAND DISCUSSION

A standard d.c. two-probe method utilizing a Vibron electrometer or a d.c. microvoltmeter according to the resistance of the specimen was used to measure the electrical conductivity. The current direction was always [loo]. Mechanically sound and electrically ohmic contacts were made to the crystals using a Johnson Matthey silver based Araldite paste. During measurement a crystal was mounted in air, in a glass tube, supported only by the electrical leads to it. Its temperature was measured by a chromel-alumel thermocouple in close proximity. The tube containing the specimen was heated by a cylindrical furnace. Measurements were made over a range of temperature from 293 to 675K by heating and cooling at a rate of $/min, readings being taken at 3 intervals. Periodically readings obtained in this way were checked by allowing the temperature to stabilize over 12 hr. These values showed good agreement with those obtained dynamically. Close agreement was also obtained between curves for heating and cooling. Successive heating and cooling runs were also carried out on given samples over several days. Again consistent agreement was obtained indicating that there was no change in a sample either from exposure to the atmosphere in which it was measured or by diffusion of silver from the contacts at the higher temperatures. The
* We are indebted to Dr. Kooy of the Philips Laboratories and Dr. Sahagain of the Air Force Cambridge Laboratories for generously donating these crystals.

Typical results of the measurements are shown in the graphs (Figs. l-3) of log o vs. l/T for a number of specimens while the complete results are given in Table 1. Several points emerge from these results. The most significant is that while an anomaly appears, as expected, at the NCel point a further discontinuity in slope appears at a lower temperature in a region approximately 390K k 10K. No such discontinuity or any other anomaly at this temperature appears to have been previously reported in NiO. In its electrical behaviour NiO may be regarded as a mixed valence semiconductor. The necessary condition for conduction is then the presence of nickel in different valence states at crystallographically equivalent sites in the lattice. The mixed valence condition can be achieved either by non-stoichiometry or by specific doping. For example, the presence of lithium or excess of oxygen in NiO provides NW sites which allow motion of holes by a thermally activated diffusion process. For small departures from perfect stoichiometry this process in NiO has been interpreted in terms of the hopping of small polarons from site to site. Because of the strong interaction of the current carries with the lattice vibrations the deformation potential at a given site must influence the electrical conductivity. KOIDE($) has suggested on the basis of conductivity measurements on lithium doped NiO that the activation energy comprises two parts. The greater part is associated with the freeing of a carrier from its self trapped site while the remainder is a small activation for mobility.

Table 1 -Before annealing


fli2-v caev

-.-.

--___

Specimen T<4OO*K (~a- er) eV


0.61 0.73

p (293K) S&m 400K < 2 < 523K (w-- ~31eV

f8 eV T > 523K

TK +a * b2

PK ca -+ 63

A.1 A.2 :a 0.57 0.58 0.56 0.62 0.60 0.58 o-47 After annealing 0.69 0.69 0.57 0.56 0.60 0.62 0.54 0.49 0.89 0.89 0.70 O-72 0.72 0.73 0.68 0.57 0.79 0.80 0.35 0.37 0.63 0.66 0.57 0.38 0.20 0.20 0.13 O-16 0.12 0.11 0.14 0.08 0.72 0.71 0.69 0.71 0.71 065 051 03% -5% 0.30 0.33 o*so 0.57 0.38 0.38

c:1 c.2 Eil

9.3 x 101 4.8 x 1012 9.5 x 106 1.2~107 1.7x107 2.4 x 107 3.7 x 106 8.3~108

0.12 0*15 0.13 0.13 0.09 011 0.07 0.04

o-15 014 0.41 0.36 0.21 0.14 0.27 0.13

39.5 403 370 364 38.5 377 373 389

518 524 535 538 526 517 538 474

7.0 x lo= l*Ox103 12x107 3.4 x 10 2.2 x 108 1.9x108 3.3 x 107 1*2x106

0.10 0.09 0.35 0.35 0.09 0.07 0.11 0.19

389 394 377 382 400 390 391 370

529 529 535 546 535 535 532 515


.Z

_~-

-.-~--.~_.-.._--

1128

M.

W.

VERNON

and

M.

C.

LOVELL

One would expect then that in an undoped crystal a magnetostrictive or crystallographic change would have a significant influence on that portion of activation energy for freeing a carrier.
ANOMALY AT 390K

The specimens have been analysed spectrographically by Johnson Matthey and no systematic impurity which could account for the kink was found. As the general behaviour of all the specimens was the same we believe the anomaly to be an intrinsic property of NiO.

In addition, the results of this spectrographic analysis, together with the fact that the crystals were grown in an oxidizing atmosphere, leads us to assume that the Nis sites arise from the presence of excess oxygen. That the epitaxial crystals have a much higher resistivity than the other samples grown at 2300K provides some confirmation of this assumption. The spin ordering phenomenon which takes place at the NCel temperature has previously been associated with a crystallographic distortion from a f.c.c. above to a rhombohedral structure below
1 Activation energy

Activation 10-7

energy

E,

FIG. 1. Conductivity

of specimen A.2 as a function of reciprocal temperature.

7 E 0 b

10-a :

x Before 0

annealing

Afterannealing

10-e x

1000
T OK

FIG. 2. Conductivity

of specimen B.l

as a function

of reciprocal temperature.

ANOMALIES

IN ELECTRICAL

CONDUCTIVITY

OF NICKEL

OXIDE

ABOVE

ROOM

TEMP.

1129

x Before annealing oAfter annealing

1000 TOK FIG. 3. Conductivity

of specimen C.l

as a function of reciprocal temperature.

523K (TN). This distortion is extremely small in NiO the cube angle being 90 3.8 at 9C, corresponding to a contraction along one of the (111) axes of 4 x 10-s A. The effect has been explained by magnetostrictive effects arising from the magnetic ordering.@?@ X-ray studies of the structure of NiO(l*~ll) have shown a rhombohedral distortion at room temperature which is not present above the NCel temperature. Little information seems to be available, however, on the actual temperature at which this distortion occurs. Some authors have reported observing cubic NiO well below the NCel point. These observations were discounted(ll) by the suggestion that the X-ray measurements were done on highly twinned crystallites which masked the rhombohedral distortion. Measurements of the thermal expansion of NiO by an X-ray technique(l2) have shown that the cubic structure appears to be established by 433K. A reassessment of the work of ROOKSBY, GILLAM and HOLDEN on NiO clearly suggests that the rhombohedral distortion has disappeared and the cubic structure has been established by 433K, probably in the range 373K-433K. Another transition metal oxide, Fe0 also shows a rhombohedral distortion below its NCel temperature. The magnitude of this distortion decreases with increasing oxygen contenW) but the temperature at which it occurs does not change. The magnitude (~-cl) of our conduction anomaly

shows a correlation with resistivity, decreasing sharply as the resistivity drops below 10s s2 cm (Fig. 4). No correlation exists between the temperature of the anomaly and the resistivity. Since the specimen resistivity depends directly on oxygen content, this evidence provides a link between the anomaly and a crystal distortion. It is believed that the crystal distortion previously associated with the NCel temperature actually takes place near 390K in NiO and causes the observed anomaly. Below this temperature the structure is rhombohedral and above it f.c.c. There are many examples in magnetic compound@) where ordering phenomena produce crystallographic distortions which also affect other properties. For example a distortion of 6% occurs in Cu Fez04 and of 15% in MnsO4. Many of these effects have been interpreted as Jahn-Teller distortions. Consideration of the crystal field splitting in NiO suggests that the small distortion here may also be explained in this way. Divalent nickel has eight 3d electrons and the free ion has a ground sF4. For NP in an octahedral environment the seven-fold orbital degeneracy is partly removed and the ground state is an orbital singlet with S = 1. This splitting is illustrated in Fig. 5 the levels being classified in the notation of Bethe. The separation of Is and I?2 is 10 04, approximately 104cm-1. The &&n-Teller theorem shows that where such a spin degeneracy exists a crystallographic distortion will occur to remove

1130

M. W. VERNON

and M. C. LOVELL

the degeneracy even in an orbitally non-degenerate state. Here the distortion can arise from admixture of Is into the ground state Is which will be of the order of h/A where h is the spin orbit coupling constant, while the corresponding multiplet

epitaxial crystal Specimen A, about 35K [Fig. 6(c)] than for the Specimens C and D, about 60K [Fig. 6(b)]. Where (es-~3) is much greater than 3 kT no hysteresis is observed but a broad transition exists [Fig. 6(a)] over a temperature range of about 80K. In contrast to (es-~1) there appears to be no correlation of (Q-Q) with resistivity, i.e. oxygen content. There is, however a significant dependence of the type of behaviour displayed at the NCel temperature, as illustrated in Fig. 6, on the method of growth of crystals. For the epitaxial crystals there is only a slight decrease of (~2--es) on annealing and the hysteresis is small. For Verneuil grown crystals the change of (Q-Q) is much larger on annealing and the hysteresis is large. Carbon arc crystals show virtually no change of (~2- ~3) on annealing and only a /-r, 3

01
103

IO"

109

IO'

I05 as a

FIG. 4. Activation energy change (~a-)eV function of room temperature resistivity.

splitting of Is will be $/A since there is no splitting in first order. The linear distortion is then given by h2
d=z+ a CO

Amio4 cm- r,
Cubic field splitting

I
Orbital degeneracy

Free ion

where a is the interatomic distance and CO the binding energy of Nis+. Typical values for these quantities are X = -250 cm-l, A = 104 cm-l, a = 4 A, EO = 2.5 eV. Substituting these values d is about 1.3 x 10-s A which is of the order of the observed distortion in NiO. It is possible then that the effect is of the Jahn-Teller type.
ANOMALY AT THE NEEL TEMPERATURE

FIG. 5. Splitting of Niz+ in an octahedral field. broad transition is observed. We associate this behaviour with the strain induced in the crystal during growing. This is minimal for the epitaxial technique; slight strains are introduced by differences in thermal contraction of NiO and MgO

There is a wide variation of (~2 -es) between different specimens (Table 1) and there is no consistent pattern in the change of (es - ts) on annealing. Some trends appear, however, when the changes occurring at TN are examined in detail. Where (es-~3) lies between 2 kT and 3 kT a thermal hysteresis is observed associated with the magnetic transition. The temperature range over which this hysteresis occurs is much less for the

substrate, but these are almost certain to be removed by annealing at 1000K. The carbon arc method seems likely to introduce maximum strain because of the relatively rapid growth rate and rapid cooling due to steep temperature gradients. Although no figures are available for the rate of growth of the Verneuil crystals, in this method growth can occur at a much slower rate and cooling is less rapid than in the arc process. We should expect that annealing at 1000K would not affect the arc crystals to anything like the same extent as Verneuil crystals. The different behaviour near

ANOMALIES

IN ELECTRICAL

CONDUCTIVITY

OF NICKEL

OXIDE

ABOVE ROOM TEMP.

1131

1000 T *K (a)

1000 TOK (h)

1000

T OK (c)

FIG. 6. Detailed conductivity in the vicinity of the Ndel temperature. (a) Specimen B before and after annealing.

(b) Specimens C and D after annealing. (c) Specimen A after annealing.

the magnetic transition illustrated in Fig. 6 may be classified then, according to the amount of strain induced in the crystal. If the behaviour of the epitaxial crystal is extrapolated, it might be expected that in a perfectly strain free crystal no hysteresis would be observed, and the value of (~2-es) would be 2 kTN.
CONCLUSION Measurements of the electrical conductivity of single crystal NiO have shown two anomalies,

Acknowledgements-The authors gratefully acknowledge the practical assistance received from J. PURCHASE and T. THOMAS,and helpful discussion with H. P. ROOKSBY. REFERENCES

near the Neel point and near 390K respectively. The magnitude of the latter anomaly &creases with increasing oxygen content of the specimen. It has been argued that this lower anomaly is caused by crystallographic distortion which is a small Jahn-Teller effect which removes the spin degeneracy of the ground state. Previously this distortion has been associated with the NCel point
and ascribed to magnetostrictive effects. The anomaly near the NCel point is thought to be due to the magnetic transition alone. Thermal hysteresis effects in its vicinity depend on the amount of strain in the specimen and a strain free crystal should show no hysteresis.

Bureau N.Y. (1961). L. 4. NACHMAN N., COJOCARU and RIBCO L., Pkys. St&u Solidi 8, 773 (1965). 5. MORIN F., Phys. Rev. 93,1199 (1954). E.. 6. CECHR., ALESSANDRINI Trans. Am. Sot. Metals 51,150 (1959). 7. KOOY C. and COU~E~WG H. J., Philips Tech. Rev. 23. 161 (1962). 8. KAN~MORIJ., @log. Tkeor. Phys. Osaka 17, 177 (1957). 9. RODBELLD. S. and OWEN J., J. Appl. Phys. 35, 1002 (1964). H.,.Actu Crystallogr. 1, 226 (1948). 10. ROOK~BY Il. SLACKG., J. Abbl. Phvs. 31. 1571 (19601. f, J. Am. &ram. Sot. 12. GILLAM k. ~~~-HoL&N 46, 601 (1963).
H. 13. ROOK~BY (private communication). 14. SUZUKIY. and ASADA E., J. Phys. Sot. Japan 16,

1. VAN HOUTENS., J. Phys. Chem. Solids 17,7 (1960). 2. KOIDE S.. J. Phvs. Sot. Jaban 20. 123 (1965). 3. BEL~V K.., Magnetic Trafisitions i. 132. Cor&tants

1785 (1961).
J. 15. GOODENOUGH B., Magnetism and the Chemical 16. JAHNH. A., Proc. R. Sot. A164, 117 (1938).

Bond. Interscience, N.Y. (1963).

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