Some Electrical and Optical Properties of

Simple Rhombohedral Boron

Cite as: Journal of Applied Physics 30, 1611 (1959); https://doi.org/10.1063/1.1735010
Submitted: 10 June 1959 . Published Online: 16 June 2004

F. H. Horn

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Journal of Applied Physics 30, 1611 (1959); https://doi.org/10.1063/1.1735010 30, 1611

© 1959 The American Institute of Physics.

 LETTERS TO THE EDITOR 1611

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FIG. 3. Second harmonic power vs pressure.
10
is approximately 0.2 mm of Hg. On the high pressure side, a larger
portion of the energy is dissipated in collisions between electrons
and gas atoms, resulting in the gas heating up. At the low pressure
end, a larger portion of the energy is being removed from the
discharge by electrons diffusing rapidly to the walls, so that more
power is required to maintain the discharge. This curve should
be affected to a considerable extent by the choice of gas and by the
geometry of the container.
The results described in the foregoing show that a gas discharge
plasma in a magnetic field exhibits a large nonlinear response to a
high power microwave signal. Best operation occurs near cyclotron
resonance on the low magnetic field side. The harmonic conversion +X 1000
efficiencies obtained compare favorably with those achieved in
crystals, but were obtained at very much higher power levels. FIG. 1. Resistivity vs inverse absolute temperature for boron. O. crystal-
line red-; Do. granular red-; D. black-simple rhombohedral boron; O.
The results are also superior to ferrite multipliers operating in the zone-refined crystalline complex rhombohedral boron with approximately
same power range.! The effects of plasma resonance place a 1018 carriers/cm3 •
practical limit on the low frequency applications of this phe-
nomenon. Going to higher fundamental frequencies should reduce
This latter curve agrees with the data reported by Greiner and
this limitation.
Gutowskj3 for boron of comparable purity. For the simple rhombo-
* The work was performed under Signal Corps Contract No. DA 36-039- hedral (red) boron resistivity measurements extended to 77 e K
sc-71053.
1 Uenohara, Uenohara. Masutani. and lnada. Proc. lnst. Radio Engrs. 45.
showed at most a doubling of resistivity from the room tempera-
1419 (1957). ture value.
'Ayres. Vartanian. and Mekhor. J. App!. Phys. 27.188 (1956).
The slope of the resistivity-reciprocal temperature curves in the
intrinsic conductivity region indicates that the thermal activation
energy for simple rhombohedral boron is larger than that for
complex rhombohedral boron. The limited optical absorption
data shown in Fig. 2 indicate that the absorption curve for

Some Electrical and Optical Properties of 104,---r--,----,---,---.---.---,

Simple Rhombohedral Boron
F. H. HORN
General Electric Research Laboratory. Schenectady. N e'1l) York (A)
(Received June 10. 1959)

10 3
W Eare reporting some preliminary results on the tempera-
ture dependence of the electrical resistivity and some
optical absorption data for boron in the simple rhombohedral
(B)

"j
structure.' The crystals investigated were some obtained originally
by the pyrolytic decomposition of boron triiodide at 1000ee. ~ I
I
These crystals are very small, about 0.2 mm maximum dimension. "" 10 2 I
I
For the electrical studies the crystals rested on a thin quartz plate
SIMPLE
supported by a graphite heater in a bottle of hydrogen. Ohmic
contracts were made by alloying pointed O.OOl-in.-diam platinum
wires to the ends of selected rod-shaped crystals. Measurements
were reproducible over the temperatures investigated.
In Fig. 1 the resistivity as a function of reciprocal absolute
temperature is plotted for representative samples of simple
rhombohedral (red) boron of two habits and for boron of the 0.6
same structure that is black presumably because of the presence
2.0
of more impurities. For comparison, also plotted is the resistivity
of polycrystalline complex rhombohedral boron obtained by zone FIG. 2. Optical absorption os frequency for boron. A and B complex
rhombohedral boron (B contains approximately 1018 carriers per em').
purification' and containing of the order of 10'8 carriers per cms, Dashed curVe simple rhombohedral (red) boron.
1612 LETTERS TO THE EDITOR

simple rhombohedral boron is shifted about 0.4 ev toward the 10'

visible from the curve for the complex form. Csing 1.6 ev for
the energy gap in the complex form of boron, the gap in simple
rhombohedral boron may be estimated to be 2 ev. IAI
It appears particularly interesting that our resistivity data
indicate that in simple rhombohedral (red) boron, impurities may
10 3 (BI
occupy very shallow levels, approximately as near the band edge
as the hydrogenic impurity levels in germanium and silicon. This
result is in contrast with those reported to date for boron. Hagen-
locker' reports levels for the donor impurities carbon and silicon
..!j
as 0.7 and 0.5 ev, respectively, while 0.6 ev is given for the acceptor
beryllium. Shaw, Hudson, and Danielson' reported similar levels 10'
for impurities in their crystals except for a small fraction in which
the levels were as low as 0.06 cv. The crvstals these authors
investigated were prepared by a method si;'ilar to the one used
to prepare our crystals. In the light of the recent recognition of the
allotropy of boron, one may speculate whether the few crystals 10 I
exhibiting shallow impurity levels were also simple rhombohedral.
\Ve have wondered based on the earlier results on energy levels-
noting particularly that the depth is about the same for different 0.6 0.8 1.8 2.0
impurities-whether the structure of boron itself precluded
shallow levels. We have presented evidence for shallow levels in Flr;.2.
simple rhombohedral boron. The same impurities may behave
quite differently in simple or complex rhombohedral boron. boron and the somewhat random polycrystallinity of present
Nevertheless, one may now speculate whether in complex rhombo- specimens. The problem should by this argument become less
hedral boron there are not shallow levels for some impurities severe as well-oriented single crystal seed becomes available. The
which in boron prepared to date have been masked by the presence growth of such boron by a Czochralski method appears to depend
of deep level impurities difficult to remove. in part on the purity of boron used. Multiple zone purification
The author would like to acknowledge L. V. McCarty as the conducted in a boat of boron nitride may be one avenue to boron
source of our simple rhombohedral boron and also to thank E. A. of the necessary purity, The system employed and pertinent
Taft for the optical results and R. O. Carlson for profitable dimensions and materials used are indicated in Fig. 1. The boron
discussion. was maintained in a protective atmosphere of helium or argon.
I McCarty. Kasper, Horn, Decker, and ~ e\vkirk, J ..-\m. Chern. Soc. 80,
The boron nitride was fired in dry hydrogen at 1500°C before use.
2595 (1958). High frequency heating (450 kc), possible if the boron is above
2 F. H. Horn, J. App!. Phys. 30,1612 (L) (1959), following Letter.
31'. S. Greiner and J. A. Gutowski, J. App!. Phys. 28,1364 (1957). about 1200°C, has been employed. Molten zone widths varied
4 A. K. Hagenlocker, "Halbleitereigenschaften von Bor," dissertation, from 1 to t the ingot length. Variation of the zone length was clue
Technischen I1ochschule, Stuttgart, 1957.
5 Shaw, Hudson, and Danielson, Phys. Re\·. 107,419 (1957).
to cracking of the ingots on cooling and the attendant difficulty
of transferring heat across transverse cracks. Cracking is not
caused by the boron sticking to the boron nitride.

Zone-Refined Boron
F. H. HORN
General Electric Research Laboratory, Schenectady, .Vew York
(Received May 13, 1959)

B ORON has been zone refined using boats made from hot-
pressed boron nitride with which molten boron near its
melting temperature does not react appreciably. Our experience
with the floating zone crystallization of boron appears to have
been similar to that of others!,2 who imply that it is difficult to
pass more than a few zones through the rods because of severe
cracking. This difficulty is probably related to the anisotropy of

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