T

ake a poll: Ask people what they

know about the element boron.
Replies will be all over the map.
Biologists will answer that boron is an
essential plant nutrient; pharmacists will
point to boric acid as an eye wash; astro-
physicists, somewhat embarrassed, will
inform us that the universal abundance of
boron is not well understood; chip mak-
ers—with pride—will point to boron’s
use in the very successful semiconductor
industry; nuclear physicists will describe
boron’s ability to moderate neutrons; and
tool manufacturers will point to the hard-
ening properties of boron.
Boron’s history, however, predates the
modern uses named above. Unverified
reports have it going back to the second
millennium B.C. when Egyptians used
tinkar, or tincal, a mineral form of borax,
for mummifying. Borax is documented to
have been used since the twelfth century
A.D. (and continues to be used) as a flux
by goldsmiths.
Today, most would be shocked to hear
of boron’s prevalence. About two million
tons of boron compounds are mined each
year, and most of them go to manufacture
borosilicate glass and fiber glass. (Boron
gives added shock resistance to glass and
better qualities to fiber glass in terms of
strength and ease of use.)
Boron is also an essential element for
detergents and bleaches, fire retardants,
adhesives, and metals alloys [1].
In spite of the tonnage of boron used in
manufacturing, there has been, until the
present, an inverse relationship between
industrial use and scientific curiosity of
boron. A routine historical search of the
published literature as far back as WWII
discovers a rather curious historical cycle
of enthusiasm and disrepute that followed 15 – 30 year cycles for silicon, germanium and silicon carbide semiconductors and
that corresponded to military/industrial cycles—the most promi- for its wide spread applications in ultrahard boron compound tri-
nent of which was the post–WWII nuclear weapons competition bological coatings such as B4C, BN, and BxCyNz alloys [3,4,5,6].
when an “anything–goes” experimental approach threw caution As with most metals and elements, it is assumed that they have
to the literal winds, and atmospheric testing was conducted with always been abundant in the earth’s crust. However, because
reckless abandon. (Check the infamous “Project Pluto” (http:// boron is produced entirely by cosmic ray spallation and not by
www.merkle.com/pluto/pluto.html). stellar nucleosnythesis, it is a low abundance element in both the
In the early days of the nuclear age, boron, as mentioned ear- solar system and the earth’s crust. Boron is concentrated on earth
lier, was significant as a neutron moderator, and boron’s high by the water solubility of its more common naturally occurring
temperature abilities led to its early industrial use by Coors Ce- compounds, borates.
ramics, which grew from obscurity to significance during this Boron exists in several allotropes, including α-rhombohedral
period by producing various high–temperature ceramics and did boron [8], α-tetragonal boron [7,9], β-rhombohedral boron,
notable pioneering work in rare–earth borides. β-tetragonal boron, γ-boron and cubic boron. α-rhombohedral
The enthusiasm/disrepute cycle – completely independent of boron, shown in Figure 1, has a unit cell of twelve boron at-
the ultimate nature of the project – has always been that boron oms. The structure consists of B12 icosahedra in which each
simply seemed determined to be unpredictably difficult and in- B atom has five nearest neighbors within each icosahedron. If
tractable to work with, operating under an idiosyncratic set of there was truly conventional covalent bonding in this structure,
rules of its own that didn’t completely conform to anything else: each B atom would donate five electrons. However, B has only
Just when it seemed about to make sense, something unexpected three valence electrons, and it is thought that bonding in the B12
would ruin the model and turn everything to nonsense. icosahedra is achieved by the 3-center electron-deficient bonds
Countless excellent scientists challenged it, but they invari- where electron charge is accumulated at the center of a triangle
ably gave up on it in furious frustration – warning those that formed by three adjacent atoms (see Figure 1) [6]. The isolated
followed to avoid it at all costs. As the years passed, however, B12 icosahedra are not stable, however, and as a result, B is not
those memories and warnings faded into oblivion, and sooner a molecular solid, however, all icosahedra in it are connected by
or later someone “discovered” that something that looked like strong covalent bonds.
it had tremendous potential, but had mysteriously been over- Pure α-tetragonal can only be synthesized as thin films de-
looked, so the cycle of curiosity and eventual enthusiasm would posited on an underlying substrate of isotropic boron carbide
start all over again. (B50C2) or nitride (B50N2), essentially an epitaxial process [6].
Boron’s neutron absorbing qualities kept it in the forefront of Most examples of α-tetragonal boron are in fact B rich carbide
research during the Cold War. This was the “Wild West Era” of or nitrides [8,9].
the Cold War with atmospheric nuclear blasts which were then
restricted to underground testing – and then a complete Test Ban
– effectively terminating and making unrepeatable much of the
experimental materials science work (primitive as it was).
But boron makes for semiconductors; and as semiconductors
replaced vacuum tubes, exponential advances in instrumentation
and in computing power ensued. With new applications of boron
unrelated to the Cold War, everyone simply presumed that work
from that earlier era could not possibly have any intrinsic value
so many decades later—and never bothered revisiting former re-
search. Besides, much of that research was classified.
Recently, however, boron research has been resurrected, pri-
marily because of its use for hardening tools. Specifically, boron
can be forced to bond with base materials and thus form a super
hard layer that resists corrosion and wear far better than the bare
tool. Boron combined with nitrogen forms boron-nitrides (BN)
that are only slightly less hard than diamond. Hardening the sur-
face of materials with boron (called boriding or boronizing) has
obvious applications to the aerospace, the oil and gas, and the
industrial cutting/boring tool industries [2].
Scientific research on boron and its allotropes has also picked
up, especially in light of exhibiting properties similar to those
of much-studied graphene. In fact, one may ask, “Is boron the
new graphene?”
Elemental boron (B) is the next door neighbor of carbon (C) in
the periodic table, and is best known for being a trivalent dopant Figure 1. Structure of α-rhombohedral and α-tetragonal boron [7].

Vacuum Technology & Coating • April 2015 www.vactechmag.com or www.vtcmag.com 39


Figure 2. Structure of β-rhombohedral boron [8].
β-rhombohedral boron has a unit cell containing 105–108 at-
oms and is shown in Figure 2. Most atoms form B12 discrete
icosahedra; a few form partially interpenetrating icosahedra, and
there are two deltahedral B10 units, and a single central B atom
[8]. Previously, it was unclear whether the α or β phase is most
stable at ambient conditions; however, gradually a consensus
was reached that the β phase is the most thermodynamically
stable allotrope [10,11]. The β phase was produced using CVD
processes by hydrogen reduction of BBr3 on hot W, Re or Ta
filaments at temperatures 1270–1550 °C [12].
The γ-phase, shown in Figure 3, has as a NaCl-type struc-
ture with two types of clusters, B12 icosahedra and B2 pairs. It is
produced by compressing other boron phases to 12–20 GPa and
heating to 1500–1800 °C, and remains stable at ambient con-
ditions [13,14]. There is evidence of significant charge transfer
from B2 pairs to the B12 icosahedra in this structure, and, in par-
ticular, lattice dynamics indicates the presence of significant long
range electrostatic interactions.
The boron compound family includes boron nitride (BN),
boron carbide (BxCy), boron carbon nitride (BxCy:N), and boron
carbon silicon nitride (BCSiN). Other borides exist but are more
Figure 3. Structure of γ-boron [13].
40 vtcmag@vtcmag.com
appropriately placed in the titanium alloy family (TiB2, TiBC,
TiBN). BN is transparent down to the near UV and cubic BN
(c-BN) is extremely hard, second only to diamond, and wear re-
sistant. This makes it an attractive material for protecting optics
and, because of its low atomic mass, it is virtually transparent to
x-rays. This material is thus an excellent protective optical coat-
ing and has high thermal conductivity [3,4,5]. Cubic BN is also
extremely resistant to oxidation, and, because of its low affinity
to steel, is used to protect cast irons and steels [15,16]. Hexag-
onal BN (h-BN) is the other common allotrope, but is soft and
unstable in oxygen and water environments.
While properties of these boron compounds are impressive,
recent results show that boron nanostructures have even more
impressive tribological and corrosion resistive properties, in ad-
dition to significant potential for hydrogen storage and electronic
device applications. Boron is now synthesized in the following
structures:
• buckyballs (fullerenes)
• nanotubes
• nanoclusters
• nanowires
• nanobelts
The first buckyballs constructed totally of B atoms have been
demonstrated and are shown in Figure 4 [17]. Unlike true, car-
bon-based buckyballs, the B molecules are not shaped exactly
like footballs. However, this novel form of boron has the po-
tential to lead to new nanomaterials and could find uses in hy-
drogen storage. The buckballs consist of 40 boron atoms and
appear to be unusually stable. Calculations and experiments re-
vealed that two stable structures exist: an almost flat molecule, a
hollow, ball-like structure made of tesselated shapes, similar to
the carbon buckyball.
Boron nanotubes (BNT) were initially developed in 2004. BN
nanotubes (BNNT) are also under development [18-21]. Tubes
Figure 4. Boron buckyball structure [17].
April 2015 • Vacuum Technology & Coating
 Figure 5. Boron nanotube with associated energy bands and sheet structure [20].
built out of the element B, shown in Figure 5, could have many Calculations showed that BNTs rolled from this boron sheet are
of the same properties as carbon nanotubes, the ubiquitous com- metallic, except for the (p,q) = (8, 0) thin nanotube, with an en-
ponents of nanoengineering [19-21]. And for some electronic ergy gap of 0.44 eV. It is noted that in the hexagonal boron ring
applications, they should even outperform C. BNT have a more of the (8, 0) thin nanotube there is a next nearest neighbor B-B
complicated structure than the simple linked hexagons that work bond, which makes the density of the thin boron tube closer to
for C, because the chicken wire pattern for B is unstable. The that of bulk boron[22] and leads to semiconducting properties.
first BNT were synthesized in 2004, and were thought to be Figure 8 shows a few typical structures and their corresponding
formed from a buckled triangular latticework. Recently it was
established that the most stable configuration for a BNT is for B
to assume the unstable hexagon lattice structure and add an extra
atom to the center of some of the hexagons, see Figure 5 [20].
Figure 5 shows the structure of the new class of boron sheet,
which is less dense than the α-B sheet [20]. After relaxation of
supercells, the B sheet remains flat and is metallic. The binding
energy per atom of this sheet, defined by Eb=[E(BS)-nE(B)]/n, is
5.93 eV, which is very similar to that of the α-B sheet (5.97 eV).
The band structure, as well as the density of state (DOS), is also
shown in the Figure. The structure as bands similar to π bands in
the graphene (see December 2011 – March 2012 VT&C ). Fig-
ure 6 gives the charge density of the boron sheet. The presence
of significant charge density at the Fermi level indicates that the
sheet is metallic.
Nanotubes are formed by rolling the B sheet and stitching it
together. Two lattice vectors are also shown in Figure 5a: pri-
mary vectors of the hexagonal lattice (a1, a2) used for CNT and
the primary vectors of the BS lattice (b1, b2). As a result of the
reduced symmetry of the B sheet, (b1, b2) vectors, which are
based on a rectangular lattice, are used to describe BNTs, and it
is more appropriate to label BNT with integer multiples of these
basis vectors [20]. The chiral vector (p, q) of the BS lattice corre-
sponds to the vector (n, m) of the hexagonal lattice with p=2n+m
and q=3m/5 (see December 2008 VT&C).
Binding energies per atom, shown in Figure 7, approach those
of BS as tube diameter increases. BNT with large diameter are
highly stable, and stability increases with increasing diameter.

Vacuum Technology & Coating • April 2015 www.vactechmag.com or www.vtcmag.com 41

 Figure 6. Charge density of boron sheet [20].
band structures and DOS. Many of these structures are metallic
with degenerate bands which make them very conductive and
potentially useful as metallic interconnects in electronic devices.
We finish with a brief description of BN nanotubes (BNNT)
[18]. The hardness of cubic BN (c-BN) is second only to that of
diamond. In addition to high hardness this material also has a
low coefficient of friction (~ 0.20). BNNTs are structurally sim-
ilar to carbon nanotubes (CNTs), and as a result, they exhibit
extraordinary mechanical properties similar to CNTs [23-25].
Despite these similarities, BNNTs are different from CNTs in
other aspects:
• Electronic properties are not sensitive to their diameters or chi-
42 vtcmag@vtcmag.com
Figure 7. Binding energy per atom (Eb/atom) of the boron nanotubes
vs the diameters [20].
ralities (compare this to the BNT above) [26,27].
• Theoretically, band gaps (~5 eV) are tunable and can even be
eliminated by transverse electric fields through the giant DC
Stark effect [28-30].
• They have high oxidation resistance [31], with oxidation resis-
tance up to 1,100°C [32].
• They are predicted to have piezoelectricity [33,34] and are ap-
plicable for room-temperature hydrogen storage [35].
• Junctions of CNTs and BNNTs [36] are expected to produce
itinerant ferromagnetism and spin polarization (see January –
April 2014 VT&C) [37].
Obviously, these properties make BNNTs very attractive
for a variety of applications in various branches of science
and technology.
Synthesis of BBNTs is challenging, and will not be addressed
here. However, fabrication techniques include arc discharge,
laser ablation, substitution reactions from CNTs, ball-milling,
chemical vapor deposition (CVD), boron oxide CVD (BOC-
VD)/floating zone method. BBNTs can be used in mechanical,
electrical, thermal, piezoelectric and optical applications by
themselves or they can be functionalized to expand their useful-
ness. Properties can be briefly summarized as:
• The axial Young’s modulus for a MW-BNNT was found to
equal 1.18 TPa, which exceeds all other known insulating
nanostructures. BNNT could also recover shape rapidly after
severe bending
• BNNTs should have a larger low temperature thermal conduc-
tivity (κ) than CNTs since they have the same phonon mean
free path as CNTs [38]. However, it is known that pure and
collapsed BNNTs have k between -18 and -46 W/mK, respec-
tively [37]. These values are far lower than the conductivity of
the sintered bulk hexagonal BN particles at room temperature
(>200 W/mK).
• BNNTs are highly resistant to oxidation. Purified MW-BNNTs
grown at 1,500°C were stable at 1,100°C in air, as shown in
Figure 9b [39] . The oxidation temperature for CNTs is 500°C.
April 2015 • Vacuum Technology & Coating
Figure 8. Geometric structure, band structure and density of state (DOS) of BNT. Below each BNT give the chiral vector (p, q) and the diameter
(D) in unit of Å [20].
• BNNTs are theoretically predicted to have merely uniform
electronic properties that are hardly modified by their chiral-
ities or diameters [40,41,42]. Moreover, zigzag BNNTs with
chirality (n, 0) are expected to have direct band gap. On the oth-
er hand, armchair BNNTs with chiral vectors (n, n) will have
indirect band gap [43]. Because of their large band gap of —5
eV, experiments using SW-BNNTs as the conduction channel
for field-effect transistors (FETs) showed that BNNTs allowed
transport through only the valence band [44].
• BNNT band gaps are tunable by doping with C[45], radial
deformation [46], or by applying a transverse electric field
across the BNNTs - the giant Stark effect [30,47,48]. BN-
NTs can either be p -type or n -type semiconductors by con-
trolling the C doping.
• BNNTs can also exhibit piezoelectricity, which originats from
the deformation effect due to the rolling of the planar hexago-
nal BN networks to form tubular structures [49]. BNNTs are
demonstrated to be excellent piezoelectric systems [50]. Piezo-
electric constant (see June 2015 VT&C) for different zigzag
BNNTs was found to increase along with the decrease of the
radius of BNNTs [50]. It has been also proposed that a (5, 0)
Vacuum Technology & Coating • April 2015
BNNT would have the largest piezoelectric constant for all in-
vestigated BNNTs
• The optical band gap of BNNTs is independent of the chirality
[51], and the photoelectric effect has been observed in them.
Unpolarized light can induce a shift current in BNNTs, with a
direction along the tube axis [52]. These photoelectric effects
can lead to new optoelectronic, optomechanical, and magnetic
applications.
While significant progress has been toward chemical func-
tionalization of conventional CNTs, similar to CNTs, BNNTs
also show promise for engineering of their properties in much
the same fashion. Additionally, the relatively wide band gap of
BNNTs restricts their use to primarily dielectric applications.
As a result, it is desirable to control the band structure of BN-
NTs in order to suit different kinds of applications. The general
pathways of functionalization of BNNTs include noncovalent
bonding via π–π interactions between polymers, covalent at-
tachments of molecules on BNNTs, and doping of BNNTs with
exotic atoms.
In this introduction we see that boron is a surprisingly unique
and extremely versatile element. It has several very useful allo-
www.vactechmag.com or www.vtcmag.com 43
Figure 9. Scanning electron microscopy image of purified BNNTs grown at 1,500°C, and (b) comparative thermogravimetric analysis curves of
BNNTs and CNTs [40].
tropes and is now being developed and used in ultrahard coat-
ings, nanostructures, including fullerenes, nanotubes, nanowires,
nanobelts and nanoclusters. Basic properties, Fullerines and
nanotubes have been addressed here. Nanoclusters constitute an
intermediate state of matter between molecules and solids and
will be addressed in the next article on boron.
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April 2015 • Vacuum Technology & Coating