Chapter 4

Nanomaterials: Fabrication

4.1 Goals
• Overview of fabrication and synthesis methods for nanoparticles.

Read:

• P. S. Hale et al., J. Chem. Educ. 82 (5), 775 (2005). Growth kinetics and modeling of
ZnO nanoparticles.

4.2 Introduction
The two basic approaches to making nanostructures involve either a top-down approach
whereby an existing solid is gradually reduced in size using some external radiation and/or
chemical, and a bottom-up approach whereby the nanostructure is built atom by atom from
scratch.

4.3 Lithography
One can start with an existing extended structure and reduce the structure using a radiation
and/or chemical. This has been used used to make quantum wires and dots. Commonly
used radiation are photon, electrons and ions. For photons, one typically uses a polymerized
organic material; for electrons one uses inorganic materials such as SiO2 . Lithography can
also be achieved via impression using a hard mold and a soft resist.

49
50 CHAPTER 4. NANOMATERIALS: FABRICATION

This process of lithography consists of a few basic steps (Fig. 4.1). A stepwise description
for a polymer resist is now given [7]:

• The resist is dissolved in a solvent to convert into a liquid form.

• The substrate is coated with the resist on a turntable (spin-coating).

• Any excess solvent can be evaporated by raising the substrate temperature (typically
around 1000 , soft bake).

• The resist is exposed to the lithographic beam.

• The treated sample is placed in a solvent in order to develop the treated resist.

• A post-exposure bake is carried out (near 1200 ) to remove excess solvent.

• A chemical is used to etch into the active layer to make the devices (transfer stage).

• The resist is removed.

Figure 4.1: Photolithographic process. Intel 45 nm SRAM cell (2006).

Some reserve the term lithography only for the sacrificial process of cutting the outline of
the future device on the resist [7].
There are at least 3 parameters of interest in lithography. The sensitivity of the resist
refers to the intensity or dose of the radiation needed in order induce sufficient modification of
the resist; a higher sensitivity will lead to a shorter exposure time. The contrast of the resist
measures the variation of the solubility rate of the developer as a function of the exposure
time; a higher contrast corresponds to a better spatial resolution of the lithographic process.
The resolution or minimum size of elements is set by diffraction effects (for photons) or
4.3. LITHOGRAPHY 51

collision effects (for electrons) since the latter effect causes blurring at the resist boundary.
Photolithography can reach down to 80 nm in resolution, deep UV to less than 50 nm, and
electron to 1 nm.

4.3.1 Transfer stage

Various processes have been developed for the transfer stage. When the structures are made
by etching into the exposed regions of the mask, this is known as subtractive pattern transfer.
When the sample is etched chemically by immersing into a solution (to which the sub-
strate is reactive but not the mask), the process is known as wet etching. The process tends
to be fairly rapid, with etch rate around microns per minute. There is also high specificity
of the etchant and the mask material. However, it is also mostly isotropic which means that
the etching can spread under the mask, leading to poor contrast; this is a disadvantage for
making nanometric patterns with vertical profiles.
An alternative is dry etching, which involves bombarding the sample with high-energy
ions (10s of eV to several keV’s). These ions knock out surface atoms via elastic collisions;
this phenomenon is known as sputtering. The efficiency of the process is quantified via the
Sigmund sputtering yield [7]
3 Ed
S= , (4.1)
4 N π 2 CU
where C = 1.81 nm2 , N is the atomic density of the material (in atoms/cm3 ), U is the
binding energy of the surface atoms (e.g., 6 eV for Si), and Ed is the energy deposited in an
elastic collision between the ion and the surface (10s of eV/nm). Ions such as Ar accelerated
to a few keV produces S ∼ 5 − 10; thus, this is a cascade process. In ion-beam etching, the
ions are normally incident which generates sharp vertical profiles. However, the process is
inherently slow. Neither is it selective (since it is a physical process not a chemical one);
hence, even the mask can be etched away. A reactive-ion etching is a combination of the wet
etching and the ion-beam etching.
When the structures are made by depositing new material into the openings in the resist,
this is known as an additive pattern transfer. The deposition is usually a physical process,
such as vacuum vapor deposition or sputtering.

4.3.2 Properties
Common types of lithography are optical, X-ray, and electron. The resolution is limited by
diffraction. A rule of thumb is that the resolution is given by
λ
D∼ . (4.2)
(2n)
If n = 1, for visible light, D ∼ 250 nm.
52 CHAPTER 4. NANOMATERIALS: FABRICATION

For an electron beam:

1.22
λ(nm) ∼ q . (4.3)
(E(eV )
Typical values are ∼ 0.04nm (at 1 keV) for the wavelength and a beam size of ∼ 1nm
When comparing the write speed: optical is parallel, e-beam is sequential; hence, the
former is faster.

4.3.3 Near-field lithography

It uses the tip-sample interaction of a near-field microscope to fabricate, e.g., nanowires. It
modifies surfaces on the atomic scale. It is not suitable for large-scale fabrication.

4.4 Epitaxial Methods

A technique that was developed in the 1970’s consists in growing crystals atomic layer by
atomic layer on a substrate. Such a growth technique is known as epitaxy. Three standard
variations are: molecular beam epitaxy (MBE) [Fig. 4.2], metal-organo chemical vapor de-
position (MOCVD), and liquid phase epitaxy (LPE). For example, instead of mixing two
components as in alloying, one purposefully segregate them. The key here is that the layers
can be made arbitrarily thin. An MBE reactor is an ultrahigh vacuum one (< 10−10 torr).

Figure 4.2: Molecular beam epitaxy for epitaxial growth. Atomically-precise layer of Fe 3 Si
on Ge (111) [APL 89, 182511 (2006)].

The elements forming the epitaxial layers are evaporated in effusion cells at the appropriate
temperature and deposit onto a substrate. Controlling the temperature and the deposi-
tion time leads to an accurate control of the layer thicknesses down to single monolayer
thicknesses.
4.5. CHEMICAL VAPOR DEPOSITION 53

The first demonstration of quantum confinement in a semiconductor quantum-well system

was on an MBE-grown GaAs/AlGaAs nanostructure. The high-quality growth is made easy
by the near lattice matching of GaAs and AlAs. Such systems also led to the discovery of
the quantum Hall effect.

4.4.1 Growth morphologies

The competition between surface free energies G of the absorbate and substrate and that
created at their interface determines the equilibrium shape of the absorbate. Thus, if

Gsubstrate > Gabsorbate + Ginterface , (4.4)

then it is less favorable to have an uncovered surface and the absorbate will wet the substrate.
Should this continue with subsequent layers to form a thin film, the growth mode is known
as Frank–van der Merwe. In some cases, competition with elastic energy due to lattice
mismatch leads to subsequent island formation — this is known as the Stranski–Krastanov
mode. If
Gsubstrate < Gabsorbate + Ginterface , (4.5)
then the absorbate favors 3D islands right away. This is known as the Volmer–Weber mode.
SK growth has been demonstrated for semiconductors (e.g., InAs/GaAsQD’s) and or-
ganics.
Another physical process is sputtering, whereby an inert gas is ionized then accelerated
to bombard and vaporize a target.

4.5 Chemical Vapor Deposition

Chemical vapor deposition uses chemical precursors to deposit nanostructures on a substrate
(Fig. 4.3). The reactor is usually either a quartz tube or a stainless steel container. Heat or
plasma breaks the precursors into reactive radicals. The radicals then diffuse and adsorb to
the substrate. Surface chemical reactions lead to the deposition of the solid. It is generally
less easy to control the growth.
Organometallic compounds are often used for making III-V compounds, when a gp-III
metal alkyl reacts with a gp-V metal hydride; the process is then called MOCVD. One
disadvantage is the use of toxic gases.

4.6 Pulsed Laser Vaporization

Pulsed laser vaporization (PLV) is an example of a bottom-up method or self-assembly
(Fig. 4.4). In this method, a laser ablates a target creating a vapor. These atoms are then
54 CHAPTER 4. NANOMATERIALS: FABRICATION

Heating

Substrate

Pump Gas inlet

Figure 4.3: CVD reactor with hot walls.

carried by an inert gas (typically Ar) to a region where they deposit and form the desired
nanostructure. For example, for growing ZnS nanowires, the target can be (ZnS)0.9 Au0.1 .
The nanowire growth itself is catalyzed, usually Au. The most common growth mechanism is
vapor-liquid-solid (VLS, Fig. 4.5), whereby the vapor diffuses into the Au nanoparticle where
it forms a liquid, and then supersaturates out of the catalyst to form the solid nanowire. We
have seen examples of such nanowires in Fig. 2.6. A related method is where the material

Figure 4.4: Pulsed laser vaporization for semiconductor nanowire growth.

of interest is thermally vaporized and then recondenses in a cooler part of the furnace.

4.7 Electrochemical Deposition

Electrochemical deposition in nanoporous template leads to metallic nanowires. Cu or Au
film is sputtered on one side of the template. The metal is deposited from solution into the
4.8. WET-CHEMICAL METHOD 55

Figure 4.5: Vapor-liquid-solid mechanism for semiconductor nanowire growth.

templates pores to form the wires. One then etches the electrode film away and dissolves the
template. The wire diameter D ∼ pore size (10nm−1 µm), the length L ∼ template thickness
(10s µm), and the quantity is controlled by the pore density (∼ 108 cm−3 ). Multisegment
is obtained by changing the deposition solution or potential during growth. Examples are
Ni-Au and Ni-Cu magnetic nanowires (Fig. 4.6).

4.8 Wet-chemical Method

Colloidal metallic nanoparticles (e.g., Au) are commonly made using this technique. As an
example of a typical reaction, we dscribe a process for making Au nanoparticles: [8]

• Boil HAuCl4 with vigorous stirring using magnetic stirring hot-plate.

• Add Na3 citrate with stirring.

• The yellow soln turns dark blue, then burgundy in mins.

• Stir another 30 mins.

56 CHAPTER 4. NANOMATERIALS: FABRICATION

Figure 4.6: TEM images of Ni/Cu multilayer nanowires. Top shows a bright-field image of
a 130 nm diameter [Ni(20 nm)/Cu(10 nm)] multilayer nanowire. Disk-shaped nickel (dark)
and copper (light) segments are clearly distinguished. Middle image shows an electron energy
loss spectroscopy map of two 30 nm diameter [Ni(5 nm)/Cu(5 nm)] multilayer nanowires.
Lower image shows an electron energy loss spectroscopy map of a 30 nm diameter [Ni(1.5
nm)/Cu(4 nm)] multilayer nanowire.

Figure 4.7: TEM image of 12 nm colloidal Au [8].