Research: Science and Education

Semimetallicity?
Stephen J. Hawkes
Department of Chemistry, Oregon State University, Corvallis, OR 97331-4003; stephen.hawkes@orst.edu

Lists of “semimetallic” elements differ. Most include all

8-
the elements (other than aluminum and beryllium) that are Ag Cu
K Sn
next to the zigzag line separating metals from nonmetals on As Sb Po
Fe
Conductors
6- Bi
the periodic table. Most exclude bismuth and selenium, and Mn

most exclude either polonium or astatine or neither but not 4-

C (graphite)

both. At one time I taught from a text that asserted that semi-
Te
metals are semiconductors, and I wondered how true that 2 - Se (gray)
was. This paper investigates the listing of semimetals. S emiconductors
Silicon and boron are often listed as both semiconductors 0-
Ge
and semimetals. As shown in Figure 1, the amorphous form

Log(Conductivity / (S/m))
Si (microcryst)
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of silicon is a nonconductor rather than a semiconductor, -2 -

whereas the microcrystalline form has a conductivity in the Si (monocryst)

ambiguous range that is neither clearly semimetallic nor

Downloaded via UNIV DE ALICANTE on September 23, 2022 at 17:38:59 (UTC).

-4 -
B (β -r hombohedral)
clearly insulating. There is no value of conductivity that can be
defined as separating semiconducting elements from insulators, -6 -
so it is meaningless to assert that microcrystalline silicon is one I
Si(amorph)
or the other. Both conduct electricity by the same mechanism, -8 -
both have conductivities that increase with increasing tempera- P (yellow)
ture (unlike metals), and both can be made unambiguously -10- Insulators
semiconducting by doping with suitable additives. Silicon and C (diamond)

boron have no metallic properties, so they are not semimetals. -12-

The metallic appearance of crystalline silicon is the usual

appearance of opaque nonmetallic crystals like iron pyrite -14-

(“fool’s gold”) and iodine. If silicon and boron are classified S (rhombic)
as semiconductors rather than insulators, then they should -16-

be classified as semiconducting nonmetals.

Selenium in its usual form, on the other hand, has
conductivity well within the semiconductor range and its
structure is one of infinite spiral chains of selenium atoms
with weak interaction of a metallic nature between the chains
(1). Its compounds mostly show a nonmetallic nature for the
selenium. The element is therefore metallic in some of its
properties but a nonmetal in others. This ambiguity defines it
as a semimetal even though it does not adjoin the zigzag line.
Arsenic is rightly classified as a semimetal in all tables
that I have seen. Its appearance is not clearly metallic or non-
metallic, it is an electrical conductor (not a semiconductor),
and its chemistry resembles that of nonmetals. Antimony is
also classified as a semimetal but the case is less compelling.
It has a metallic appearance (Aesar describes it as a bluish-
white metal [2]), it is more brittle than most metals, and it
is an electrical conductor outside the range of semiconduc-
tors. It forms a few cationic compounds, so its chemistry is a
little more metallic than that of arsenic. It is reasonable to
classify it as a semimetal but it would also be reasonable to
classify it as a metal. This brings us to bismuth.
The case for classifying bismuth as a semimetal is stronger
than for antimony, but that makes it an exception to well-
known trends, which is probably why it is usually classified
as a metal. Being to the left of polonium in the periodic table,
bismuth would be expected to be more metallic than polonium
but is actually less so. Bismuth forms more cationic compounds
than antimony, but fewer than polonium. It does not adjoin
the zigzag line. While its neighbor polonium is unambiguously
Figure 1. Log of electrical conductivity in S m᎑1 at 25 °C. All the
semiconducting and nonconducting elements of which the conduc-
tivity is known are included, and sufficient conducting elements to
illustrate the range. The values are the reciprocal of the resistivities
given by Emsley (11) except for the value for polonium, which is
calculated from Maxwell’s (12 ) value 4 × 10 ᎑5 Ω cm at 0 °C
(correction for temperature does not change the first significant fig-
ure in this case) and for the three forms of Si from refs 13–16 .
a silvery-white metal (3, 4), bismuth has a less clearly metallic
appearance. Aesar describes it as “gray with a reddish tinge”
(2) and the CRC Handbook describes it as “a white crystalline
brittle metal with a pinkish tinge” (5). It is less electrically
conducting than either antimony or arsenic (see Fig. 1), both
of which are usually classified as semimetals, or than polonium,
which is a metal and a conductor, or than most other metals.
With the exception of mercury, bismuth has a lower thermal
conductivity than all other metals (2). These properties require
bismuth to be classified as a semimetal although it is separated
from the zigzag line by polonium, which is not a semimetal
but a metal.
Of the other elements next to the zigzag line, beryllium
and aluminum are metals, and it has been shown elsewhere
(6 ) that polonium and astatine are not semimetals but are
respectively a metal and a nonmetal. The line is therefore a
misleading guide to which elements are semimetals. The prac-

1686 Journal of Chemical Education • Vol. 78 No. 12 December 2001 • JChemEd.chem.wisc.edu


tice of calling Si, B, Po, and At (and perhaps Sb) semimetals,
but not Se or Bi, is thus more deceptive than informative.
The most easily defensible listing of semimetallic elements
is Ge, As, Se, Te, Sb, and Bi. If Bi is omitted, as is traditional,
then logic requires that Sb also be omitted.
Definition of “Semimetal”
Several scales have been proposed which give values for
semimetals that are intermediate between those for metals
and nonmetals, suggesting that semimetals may be recognized
from their position on the scale. Electronegativity (7), average
valence electron energy or an electronegativity derived from
it (8, 9), and the ratio of molar refractivity to molar volume
(10) have been proposed. Anomalies can be found for each
of these scales and they do not identify the same elements as
semimetals. Metallic character is a combination of several
properties, so it is more useful to judge semimetallicity sepa-
rately for each element.
Periodic Table
Rather than defining a list of “semimetals”, it may be
more useful to print three-dimensional periodic tables or
diagrams similar to Figure 1, showing the variation in prop-
erties that are associated with semimetallicity. These may be
electrical conductivity, hardness, average valence electron energy,
reflectivity, the energy gap between the conductance and valence
bands, or any other relevant property. This will be more
informative than using the undefined (and possibly unde-
finable) term “semimetal”.
A diagram similar to Figure 1 appears in Edwards’s
paper (17 ). The conductivity shown there for diamond is a
millionfold lower than Emsley’s value shown here.
JChemEd.chem.wisc.edu • Vol. 78 No. 12 December 2001 • Journal of Chemical Education
Research: Science and Education
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