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CHALLENGES IN NANOMATERIALS DESIGN

A. S. Edelstein,* J. S. Murday and B. B. Rath
Naval Research Laboratory, Washington, DC, 20375, USA

CONTENTS
1. INTRODUCTION 5
2. ADVANCES IN FABRICATION/PROCESSING 5
2.1 Bulk Fabrication/processing 5
2.2. Film Fabrication/processing 6
3. ADVANCES IN CHARACTERIZATION 9
3.1. Tunneling 10
3.1.1. Scanning tunneling microscopy 10
3.1.2. Scanning tunneling spectroscopy (STS) 10
3.2. Field Emission 12
3.3. Force Microscopy/spectroscopj 12
3.4. Near-jield Microscopylspectroscopj 13
4. PROPERTIES 14
4. I. Mechanical Properties 14
4.2. Surface Properties 16
4.3. Electric Transport, Electronic and Optrcal Properties 16
4.4. Magnetic Properties 17
5. CONCLUSION 17
ACKNOWLEDGEMENTS 18
REFERENCES 18

1. INTRODUCTION
When crystalline dimensions are reduced to nanometre sizes, new structures and properties
result. Because of this, considerable effort is being devoted to fabricating nanomaterials
to exploit their special properties. Here we present an overview of some aspects of these
efforts. The field of nanomaterials is very large and can be considered to include clusters
and, in fact, any material having a nanometre dimension. Because of space limitations, no
attempt has been made to provide a comprehensive overview. A recent book provided such
an overview.“’ Although the choice of materials to be discussed was of necessity subjective,
the emphasis will be on selected advances in fabricating and characterizing nanomaterials
and their properties. We begin with a discussion of advances in fabrication/processing of
nanomaterials.

2. ADVANCES IN FABRICATION/PROCESSING
2.1. Bulk Fabrication/processing
As in all areas of materials research, progress in the study of nanomaterials is dependent
on having new materials that are worthy of study. There is a need for different techniques

*To whom correspondence should be addressed.

5
6 Progress in Materials Science

to fabricate the various kinds of nanomaterial, including bulk material composed of

nanometre-sized particles. (2.3)For example, thermomechanical processing (an example is
given in Section 4.1) and mechanical attrition can be used to produce bulk nanomaterials.
Vapor deposition (chemical, physical, laser, etc.) conditions can be arranged to grow small
grains.(4) The same is true for solution deposition (sol-gel, electrochemical, etc.) of
precipitates. w The fabrication of free-standing powders of nanometre size has been
done through atomization technique,@*‘) and by growth from a supersaturated vapor@+
obtained by limiting the mean free path in an inert gas.
Material transformations through reactions using chemical precursors can readily
produce nanostructures in bulk quantities. For example, the sol-gel process was employed
to make nanostructures.‘“) In this process, glassy structures form in which nanometre-sized
voids may contain other materials. Subsequent chemical and physical treatment of these
sol gels can lead to bulk quantities of material containing the gel, with or without
inclusions, having the desired grain sizes. Thermodynamic drivers for the production of
certain chemicals are reasonably well understood, although the kinetic principles leading
to a desired morphological structure from chemical reactions are less well understood. This
represents an interesting area for research. Control of morphology may lead to highly
desired properties.
Another fabrication method is known as ‘self-assembly’. This refers to the
thermodynamic and kinetic processes that lead to an ordered product. Nanocubes of
MO self-assemble in the vapor (‘*)to larger n x n x n cubes with n = 2, 3 and 4. Fullerenes
self-assemble into clusters with magic numbers that are probably due to the formation
of icosahedra similar to those found for Ar clusters. (14)Another approach of interest
is the use of vesicles (self-assembled lipid layers in spherical geometry) to cover
nanostructures. This cover prevents coagulation and ripening processes until the latter
stages of processing. (Is)Understanding the complex interplay between thermodynamics and
kinetics to take advantage of nature’s processes is a challenge. There is a need to achieve
predictability. Methods using the self-assembly of molecules(‘6~‘7)are eliciting considerable
interest, especially in the biomolecular engineering disciplines.

2.2. Film Fabrication/processing

Reducing the size of semiconductor structures is one of the most intensely pursued high
technology areas today. Decreasing the device sizes generally increases the speed while
diminishing the cost and power dissipation per operation. Device size scales have already
been reduced to nanometres in one dimension through the use of molecular beam epitaxy
(MBE) and organometallic vapor phase epitaxy (OMVPE). Atomically smooth films can
be produced with thicknesses ranging from nanometres to micrometres.“*’ This fine
control enables electronic band gap engineering through the fabrication of suitable
multilayers or superlattices and represents a highly flexible approach to materials by
design.(‘g.20)Current electronic devices (quantum well lasers, high electron mobility
transistors, resonant tunneling diodes, etc.) already utilize these nanodimensioned films.
Further changes from bulk properties are expected when additional dimensions are
decreased; e.g. smaller second (wire) and third (dot) dimensions. The fabrication of these
structures with the necessary control of composition/structure/geometry is not readily
accomplished.
 Nanomaterials Design 7

Microfabrication techniques for electronic structures are commercially viable at the

0.35 urn scale (for example, the Pentium Pro chips). Meanwhile, laboratory techniques are
focused on solving problems with fabricating 0.1-0.25 urn features. The fabrication
of sub-micrometre or nanometre dimensions in one (wire) and zero (dot) dimensional
structures generally utilizes lithographic processes. (*‘,**)Visible/UV light is typically used
because it can produce accurate patterns simultaneously (parallel processing) across an
entire wafer of 8 to 12 in in diameter; as structures become smaller, visible/UV light
lithography becomes diffraction limited. Phase contrast techniques have extended the
optical lithography to sub-micrometre dimensions’*‘) and, thereby, have extended
visible/UV manufacturing lifetime. Anticipating an ultimate limit to the use of those
wavelengths, X-ray techniques are being investigated. (24’ Additionally, high-energy
electron/ion beam projection techniques are known to give nanometre resolution exposure
to resists.“‘,**) Proximal probes enable lithography with nanometre resolution by using
lower energy interactions. (25-27)These techniques can construct material structures
atom-by-atom’*‘,**’ or write nanometre-dimensioned patterns.(2”33) An example of a
functional nanostructure made with an atomic force microscope is shown in Fig. 1. The
figure is an atomic force microscope (AFM) image of a single, atomic-sized, metallic,
point-contact, room-temperature, quantum device. An electrically conducting AFM was
used to anodically oxidize selected regions (raised light areas) of a 1 urn wide Al wire. A
second oxide feature, highlighted by the circle, further constricts the current down to a
channel approximately one atom in diameter. Other approaches to the synthesis of
nanomaterials are discussed in considerable detail in a recent book.“)
Parallel processing is an economic necessity for commercial fabrication. While high-
energy electron beam exposures are capable of defining structures of 10 nm, currently this
method is neither robust nor fast. Writing with proximal probes is presently also performed
in serial fashion, but several attempts are being made to develop microfabricated arrays
which might introduce as many as lo4 writing heads per square inch.‘3s-37) A major concern
with the proximal probe approach is that the probe itself might become changed or
damaged due to contact with the writing surface. As a middle ground between proximity
and high-energy electron patterning approaches, microfabrication by moderate voltage
(1 kV) electron beam sources are under investigation.‘38,39’
Lithographic masks have been typically made by patterning and etching. An interesting
alternative under investigation is nanochannel glass. (40’It is found that, by drawing bundles
of concentric glass tubing over multiple cycles, and by carefully arranging the glass bundles
in each draw, surprisingly regular arrays of holes can be fabricated in a glass wafer. The
dimensions of the holes in these wafers have been as small as 30 nm. Figure 2 shows an
example of an array of these channels which might serve either as a template for molecular
diffusion to a backing plate (mask) or for deposition of quantum dots/wires into the pores
themselves.
Resist technology at the micrometre scale has utilized polymers. But for very thin
films, self-assembly of supramolecules may be a more effective approach; e.g. with
appropriate chemicals such as surfactants, a two-dimensional layer of monomolecular film
readily forms at the surface of a liquid. The familiar Langmuir-Blodgett technique
captures this film on a solid plate. Self-assembly of remarkably defect-free films onto a
substrate directly from a gas or liquid under ambient conditions is possible. Several groups
are investigating these materials for application in patterning and processing of nanoscale
structures.‘4’-43’
 Progress in Materials Science

(a)

20

10

(b) 8

200 300
Time (Set)
Fig. 1. (a) An AFM image of a quantum device fabricated by use of an electrically conducting
AFM as described in the text. (b) The graph plots the conductance of four different trials of the
device, which were recorded in real time during the fabrication of the point contact. A final
conductance of 2ez/h was achieved, which corresponds to a single atomic-sized conducting channel
(conductance value of one).co
 Nanomaterials Design 9

Fig. 2. SEM micrograph illustrating the uniform hexagonal array of 0.5 pm diameter channels in
a nanochannel glass.

3. ADVANCES IN CHARACTERIZATION
This section highlights the new tools that have become available for characterizing
nanostructured materials, with emphasis on the new class of analytical tools-proximal
probes. These are analytical tools in which the separation between the probe and the
sample is a few nanometres. c-61 The scanning tunneling microscope (STM) is the most
recognized example of a proximal probe. Such probes can be organized into four classes
defined by the physical principles on which they operate-tunneling, field emission, force,
and near-field. CM)The operating p rinciples and capabilities of these proximal probes are
succinctly presented below with copious references (4657)for those desiring more extensive
understanding. A Workshop on Industrial Applications of Scanned Probe Microscopy
focused on accelerating the already rapid rate at which proximal probes are being
incorporated into industrial practices.(58)
In addition to the proximal probes, other advances in analytical capability are
important. Low-energy electron microscopy with better than 10 nm resolution has been
developed by Bauer.‘j9) Ourmazd et al. (60)have combined chemical lattice imaging with
vector pattern recognition to extract near-atomic composition profiles by means of
transmission electron microscopy (TEM). Konnert and D’Antonio(61) have shown that
electron nanodiffraction patterns may be obtained with scanning transmission electron
10 Progress in Materials Science

microscopy (STEM) beams. These diffraction patterns, which change drastically when the
beam is translated a small fraction of its diameter, contain information on the structure
of the atoms within the beam to a much higher resolution than the beam dimension. The
electron nanodiffraction patterns obtained with a STEM from overlapping regions of an
Si (110) sample have been used to reconstruct 1 8, resolution images.(62) With the
high-intensity synchrotron X-ray sources, the size of crystallites necessary for X-ray
diffraction studies is in the nanometre domain (0.4 l.tm3).(63)

3.1. Tunneling
3.1.1. Scanning tunneling microscopy (STM)
Scanning tunneling microscopy is based on electron tunneling through the potential
barrier between two surfaces positioned about a nanometre apart. The exponential
dependence of tunneling current on tip-surface separation imparts the ability to image the
surface with nanometre resolution. Valuable resources for scanning tunneling concepts and
for the state-of-the-art are STM conference proceedings(45) and several books.(4657)
Tunneling contrast mechanisms at clean (UHV) metal and semiconductor surfaces are
believed to be reasonably well understood. (5’.40Moreover, tunneling is not constrained to
vacuum barriers, and can occur through dielectric fluids. Tunneling tips are utilized in the
in situ study of electrochemical phenomena, .(61*65)however, the contrast mechanisms at the
solid/liquid interface are not always apparent. The tunneling tip also can be used to image
buried interface structures in a technique called ballistic electron emission microscopy
(BEEM).‘%’
There have been several efforts at microfabricating an STM apparatus;(36,37)MacDonald
and co-workers at Cornell have demonstrated an operating microfabricated STM with
5 MHz resonant frequency and 400 nm x 400 nm scanning range.@‘)The principal drivers
to the microfabrication efforts are lithography and non-destructive evaluation (NDE) of
integrated circuits. Moreover, these microfabricated proximal probes will enable
investigation in highly constrained geometries.
An elegant example of STM imaging to assist in understanding semiconductor
surface structures at the atomic scale is presented in Fig. 3. The figure compares the
experimental and theoretical STM images of Si(5 5 12) which were used to determine
how the surface reconstructs. However, meaningful characterization of surface
features does not always require atom-level resolution. Many groups utilize the
STM for characterization of high-technology nanometre structures such as machined
surfaces,(69*‘O)fracture surfaces,(“) Vickers’ imprints, (72)X-ray optical multilayer films,(73)
microfabricated electronic device patterns,(74) optical disks(75) and microbridges in
superconductivity quantum interference devices (SQUIDS).“@

3.1.2. Scanning tunneling spectroscopy (STS)

In addition to imaging, it is also possible to hold an STM tip over a specific location
and measure its tunneling current-voltage characteristics. A tip-sample potential range
approaching 4 V is possible before the tunneling approximations are violated. When the
tip is biased negative, the tunneling electrons originate in filled states of the tip and tunnel
into the empty states of the surface and vice versa for reverse bias. The current versus bias
data therefore yield a convolution of the tip and surface electron density-of-states. This
 Nanomaterials Design 11

Fig. 3. The atomic-scale structure of Si(5 5 12). Models are shown of the bulk-truncated (D) and
reconstructed surfaces (C). The atoms are shaded to highlight their proposed rearrangement within
the reconstruction. The unit cell on the reconstructed surface is indicated (black box). Theoretical
(A) and experimental (B) STM images of reconstructed surface are exhibited.‘68J

spectroscopic capability has been used to investigate the site-specific, surface-state

character of numerous surfaces.(“)
STS is limited as a chemical analytical tool since the valence electron density-of-states
is too broad for atom-specific identification, unless one already knows a great deal about
12 Progress in Materials Science

the surface under investigation. There are some efforts to couple electromagnetic
spectroscopies for chemical identification and tips for localization.(7*,79)

3.2. Field Emission

Significant electron tunneling current occurs only when the tip and surface are close
(-0.5-2.0 nm) and at low bias conditions (< 4 V). As the tip and surface separation is
increased and/or the bias is raised, electron transfer occurs under the field emission
approximation.“‘) Field emission tips are commonly used in scanning electron microscopes
where their high brightness, low-temperature operation and small source volume enable
high-resolution work. Spot sizes of OS-5 nm are achieved with working potentials in the
range OS-50 kV. If the tip shaping techniques used for field ion microscopy are used, then
the field emission half-angle can be very small. (8’,82)
Electron beams from these sharp tips
placed close to the surface (N 10 nm) can have spot diameters in the tens of nanometre
range with biases in the range of 10 to 100 V. Compared with conventional scanning
electron microscopy (SEM), the lower electron energies give greater surface sensitivity and
diminished beam damage. Compared with STM, the higher electron energies enable core
electron spectroscopic analysis of the surface species.
Microfabricated field emission electron guns(38*39) may enable the construction of very
small electron microscopes. It is conceivable that we may place a future microfabricated
SEM directly onto a sample for analysis, rather than be required to cut off a piece of the
sample for insertion into a vacuum chamber.

3.3. Force Microscopy/spectroscopy

A limitation to STM/STS and its field emission cousin is the requirement of a large
electron current density. To use these techniques, the sample must be reasonably
conducting. To overcome this limitation, Binnig et al. (83)developed the concept of atomic
force microscopy (AFM). The basic idea is to measure small deflections at the end of a
thin cantilever beam; the beam deflection is induced by the forces between a sample and
a tip on the free end of the cantilever. If the beam is either microfabricated or a fine wire,
then small spring constants (0.1-100 N m-‘) are possible. For 0.01 nm displacement
sensitivity, forces of 10e8 to lo-‘* N are measurable (specially constructed force
microscopes have measured as low as 1O-‘5N). These AFM-measurable forces are
comparable to the forces associated with chemical bonding, e.g. N lo-’ N for an ionic
bond, * lo-” N for a van der Waals’ bond and N lo-‘* N for surface reconstruction.
Many variants on force microscopy have been developed(46*53,5s’s6) and several are
commercially available. The AFM techniques have been widely employed for probing
surface forces and mechanical behavior,‘8”87’ imaging samples with low electrical
conductivity,‘88) and for probing biological structures. (89,90)
Under selected conditions in the
contact mode, i.e. the sample in physical contact with the tip, the AFM has produced
images with atomic resolution.(9’)
The potential for atomic force microscopic technology to provide revolutionary new
insight is illustrated by the recent measurements of Lee et aZ.@“).Utilizing atomic force
microscopic concepts, they have directly measured the binding forces associated with DNA
molecular recognition. Previously those forces had to be deduced from thermodynamic
(ensemble averaged) measurements of binding energies. The left side of Fig. 4 has an
 Nanomaterials Design 13

Microscope Probe I ‘ I ” ’” ,’ x ” ” ”

Fadhesive = 2.3 nN

0 20 40 60 80 100 120 140 160

Relative Surface Separation (run)

Poly-inosinc (I) linked to Force required to uncoil a

surfaces by base-pairing single poly-inosine strand and
with complementary cytosine (C) break the base-pairing interactions
Fig. 4. Atomic force microscope measurement of the binding force between complementary
strands of DNA. (A) Schematic of tip/surface linkage by complementary DNA molecules.
(B) As the tip is moved closer to the surface, there are very low forces until physical contact
is made (the vertical spike at zero separation). On retracting the tip, the large negative force at
25 nm separation indicates full chain extension. The maximum force is a direct measure of the
DNA bond strength.

illustration of strands of poly(cytosine) (a nucleic acid) covalently attached both to a

substrate and to a force microscope tip. When strands of poly(inosine) (a nucleic acid
complementary to cytosine) are introduced into the solution immersing the tip and
substrate, the two complementary strands can pair as shown in the illustration. This
binds the tip and surface together. The right side of Fig. 4 shows the force measured
as the tip is first brought into contact with the surface and then withdrawn. As the tip
recedes from the surface, initially there is a very low attractive force which increases
non-linearly. The low attractive force is due to unraveling of the long poly(inosine)
strand. When the strand is fully elongated, the binding force becomes much larger.
Further retraction causes the cytosine/inosine linkage to fail and the cantilever is then free
to return to its equilibrium position. With some improvement in signal-to-noise ratio,
this technique should be able to probe the forces associated with the chain unraveling.
Such a capability will be extremely useful for resolving the current debates on protein
folding.

3.4. Near-field Microscopy/spectroscopy

The most developed variant of near-field microscopy/spectroscopy utilizes the optical
spectrum. Optical images with a resolution below the diffraction limit of light can be
obtained if a small aperture is located close (near-field) to an object.(46,53)In the visible
14 Progress in Materials Science

spectrum, features with resolution of about 10 nm laterally and 1 nm vertically can be

obtained. It has been shown that it is possible to detect the fluorescence of a single molecule
with this technique.(92)

4. PROPERTIES
4.1. Mechanical Properties
The mechanical properties of nanostructures such as the strength are dominated by
the interfacial properties of these structures. For example, ultimate failure results from
crack nucleation and migration, which frequently takes place along interfaces. Because
of the large number of interfaces, the bulk properties of nanomaterials such as their
strength and toughness are significantly modified. (93)It is well established that materials
with smaller grain sizes (down to about 100 A) are stronger. The usual mechanisms of
plasticity and failure do not adequately represent a sample largely made up of grain
boundaries.
The strength of materials can be increased by introducing barriers or inhibitors to delay
or reduce the crack migration process. Composites which introduce barriers to slip and
crack migration within a matrix operate on this principle. Nanostructured composites offer
an increased density of inhibitors to slip crack migration, leading to enhanced mechanical
properties. A large percentage of material is in the interfacial layer when the surface layer
thickness is comparable to the crystallite size. The fraction of the material in the interface
is 3dr/r where dr is the interface thickness of a sphere with radius r.
Interfaces in crystalline solids also play a role in high-temperature creep. Since one of
the predominant mechanisms of creep, grain boundary sliding, results from migration of
grains along the grain boundary, a material that is largely made up of grain boundaries
will exhibit greater creep rates leading to superplasticity. This may or may not be desirable.
For example, ceramic nanostructures are found to be more malleable, or ‘superplastic’.
Thus, the formability of ceramic materials is enhanced with nanostructures. However,
metallic nanostructured materials, formed from metals that are malleable when they have
micrometre-sized grains, may have unacceptable levels of creep. This is especially likely
to be a problem if these metallic nanostructured materials are subjected to temperature
excursions.
Improved mechanical properties have been realized for selected nanomaterials.(94)
Direct attempts with other materials to demonstrate the improvements for structural
application have met either with prohibitive cost or technological barriers. Laboratory
techniques used to demonstrate the behavior of milligram or gram samples are of
value to show feasibility of these new materials; however, to be incorporated into
technology, sufficient quantities of material must be produced at a market-acceptable
cost.
Many investigations of the mechanical behavior of materials require bulk quantities
(pounds) of material. The problem of having small quantities of material for testing
can be mitigated somewhat by using techniques such as nanoindentation. Obtaining
quantitative information by this technique has been difficult but there has been recent
progress(95)with the use of spherical indentors. Figure 5 shows a plot of the reduced elastic
modulus obtained from nanoindentation measurements with spherical indentors on
polystyrene films as a function of film thickness. The reduced modulus is an average
 Nanomaterials Design 15

0
0

0 I 8 I n I ’ 1 ’
0 200 400 600 800
Film thickness (nm)
Fig. 5. Measurements of the elastic moduli of thm. polystyrene films on Si obtained by using
spherical indentors. The reduced elastic modulus is an average modulus taking mto account the
deformation of the tip and the sample. The bulk value is indicated by the straight hne. The
deviation at low film thickness is due to tip deformation.

modulus taking into account the deformation of the tip and the modulus. One sees
quantitative agreement between the literature value and the reduced modulus determined
by the nanoindentation measurements on thicker films for which tip deformation is less
important.
By controlling the thermomechanical processing history of a sample, the grain size
may be modified to a surprising degree. A notable example of the application of this
approach is the nanostructured composite composed of COWC.‘~~’This material exhibits
a hardness that makes it attractive for machine cutting tools. Rapid solidification with
controlled processing conditions and chemical composition produces grain structures over
a wide range, from being similar to glasses to submicrometre-size crystallites. This is not
a simple process to control. Rapid cooling rates may not result in a nanostructured
material, but slow cooling rates always produce relatively large grain sizes.
The admixture of nanostructures with a matrix material (organic, metallic or ceramic)
leads to a variety of composite materials having superior properties. The discovery of
carbon tubules having nanometre dimensions’97’ indicates the vitality and continued
opportunity for the unexpected discovery of new nanometre-sized materials. These
nanotubes of carbon appear to have surprising mechanical properties. They may offer
improved material properties once researchers successfully demonstrate cost-effective
methods of synthesis and fabrication.
The ability to fabricate microstructures using lithographic techniques has been extended
to the fabrication of machines consisting of moving structures, gears. levers, etc.,
characteristic of larger devices. (98,99)
A 10 urn gear, however, takes considerable expertise
to fabricate and control. The community of micromechanical electromechanical machines
(MEMS) is demonstrating a great deal of ingenuity for fabricating mechanical devices and
sensors (on a chip) using lithographic techniques. This innovative field has demonstrated
cost-effective alternatives for a number of sensors.
16 Progress in Materials Science

4.2. Surface Properties

An inherent property of nanostructures is the reduced variation in surface roughness
as well as crystallographic texture. Whatever the material, particularly when grown from
the vapor phase, a surface is usually uniform only to the dimensions of the grains or
sub-units from which it is composed. Materials with smaller crystallites can lead to
improved machinability and surface finish which, for hard to machine materials, provides
a significant fabrication advantage. (‘O”)This feature of the nanocrystalline aggregates is
particularly important for diamond films. The recent discovery of new processes to prepare
diamond without the usual application of high temperature/pressure has offered many new
opportunities. (lo’)Nanostructures of diamond crystals adhering to each other and to a
surface have become recognized as an important adjunct to modifying the properties of
surfaces. Nanocrystalline diamond films can be used for many industrial applications
without major polishing requirements. Research is underway to formulate advanced
composites with diamond as a second-phase particulate.

4.3. Electric Transport, Electronic and Optical Properties

The electronic and optical properties of nanomaterials differ from those extrapolated
from larger dimensions. Potential barriers along the transport direction or as boundary
conditions introduce major perturbations which modify the waves and can lead to
new phenomena. These effects are important for structures having dimensions of 10 nm
or less.
Resonant tunneling transistors (RTTs) have been proved to be high-speed devices with
a useful negative transconductance,(‘02) and are likely to become important commercially.
These devices are fabricated by using the close tolerances of atomically smooth layers
grown by molecular beam epitaxy, and are referred to as vertical structures (the transport
is perpendicular to the plane of the surface). The negative transconductance exhibited with
RTTs can be demonstrated with many alternative geometries, including those with fingers
serving as a transistor gate, which produces an alternating potential energy field to the
migrating charge carriers.
Confinement effects modify the electron energy levels much as the quantized energy
levels for a particle in a box. The band gap is typically increased in smaller structures,
causing a blue shift. (‘03)Some nanomaterials are lasing media with high gain and/or have
large non-linear susceptibility coefficients. Usually the dimensions of these nanostructures
are such that light is scattered minimally at the boundaries, hence optical transmission
through composites can be high; in which case, the composites appear as transparent (or
colored) materials. However, by using the nanochannel glass discussed above, it is possible
to observe two-dimensional photonic band behavior in the visible.““’
Another phenomenon, the Coulomb blockade, is due to the discrete nature of electric
charge. As charge carriers migrate along nanostructures, they charge capacitors which are
so small that the presence of a single electron has a substantial influence on the voltage
across the capacitance. This, in turn, influences the transport of additional charge carriers
to that location in space; hence strong correlation effects are observed at low temperatures
with these small structures.“Os’ There have been some reports of possible effects at room
temperature,“06’ when charge migration across a small dielectric (such as a molecule
between a tunneling tip and a surface) is observed.
 Nanomaterials Design 17

-40

-50 - -13
-50 -30 -10 10 30 50
H(kOe)
Fig. 6. The longitudinal (II) and transverse (I) magnetoreslstance, p. of a granular Co,,Ag,,, film
annealed at 500 K. (From 13”.p. 368.)

The electric transport properties of nanomaterials also can be unusual. Doped

nanophase ZnO(B,Bi,Co,Cu,Sb,Sn) with 3-10 nm grains has demonstrated varistor
behavior for voltages of up to 30 kV cm-‘.(‘07’

4.4. Magnetic Properties

Magnetic properties of nanostructures likewise provide a fertile ground for new
discoveries. Thin layers of magnetic materials such as iron, in conjunction with
chalcogenides in intervening layers, show evidence of high anisotropies and internal fields
perpendicular to the plane, just the opposite of that expected from other materials. These
materials show a large resistance change as the magnetic field is changed
(magnetoresistance),“‘*’ and appear to be promising for improved detectors in recording
devices. Some multilayer(‘W’ and granular samples”“, ‘I’)exhibit giantic magnetoresistance.
Figure 6 shows an example of this phenomenon. These materials are being studied
intensively for use in magnetic recording read heads. They also exhibit important
properties required for non-volatile memory devices. Additional, unexpected magnetic
behavior appears in other materials. The interplay between magnetic effects and transport
properties introduces an interesting potential for magnetically driven electronic devices.

5. CONCLUSION
In summary, the advancing frontier of nanoscience and nanotechnology appears to offer
exciting scientific challenges and possibilities. The rapid progress in nanomaterials is
clearly evidenced in the exponential increase in published work during the last five years.
Many related programs will be needed to maintain this progress and to investigate the
18 Progress in Materials Science

validity of hypotheses, many of which are difficult to test. Often it is only by applying
several techniques that one can understand the structure and properties of a new
nanomaterial. If present nanomaterial processing techniques are refined and new ones
developed, the interplay of new ideas in this frontier will be attractive for some time to
come.

ACKNOWLEDGEMENTS
Useful conversations with W. Tolles, R. Tonucci, and B. Shanabrook and the support of
the Office of Naval Research are gratefully acknowledged.

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