ENMT807951

SYNTHESIS AND FABRICATION

OF TWO-DIMENSIONAL (2-D)
NANOSTRUCTURES

2
Introduction
Film growth can be generally divided into two groups:
Vapor-phase deposition: for examples evaporation,
molecular beam epitaxy (MBE), sputtering, chemical
vapor deposition (CVD), and atomic layer deposition
(ALD).
Liquid-based growth: for examples electrochemical
deposition, chemical solution deposition (CSD),
Langmuir-Blodget films, and self-assembled
monolayers (SAMs).
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Fundamentals
 Growth of thin film involves the processes of nucleation
and growth on the substrate or growth surfaces.
 Nucleation process plays a very important role in
determining the crystallinity and microstructure of the
resultant films.
 Nucleation in thin film formation is a heterogeneous
nucleation, in which the size and shape of initial nuclei are
assumed to be solely dependent on the change of volume of
Gibbs free energy due to supersaturation, and the
combined effect of surface and interface energies governed
by Young’s equation.
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Nucleation Modes
 Island or Volmer-Weber growth: occurs when the growth species
are more strongly bonded to each other than to the substrate. Many
metals on insulator substrate, alkali halide, graphite and mica
substrates show this type of nucleation during the initial film
deposition.
 Layer or Frank-van der Marwe growth: here growth species are
equally bound more strongly to the substrate than to each other. The
most important example include epitaxial growth of single crystal
films.
 Island-layer on Stranski-Krastonov growth: This is an
intermediate combination of layer growth and island growth. This
mode typically involves stress, which developed during the formation
of nuclei or films.

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 Nucleation Modes, cont…
 Schematic illustration of three basic modes in initial nucleation: Island or
Volmer-Weber growth; Layer or Frank-van der Marwe growth; Island-layer on
Stranski-Krastonov growth

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Nucleation Modes, cont…
For island or Volmer-Weber growth the contact
angle must be larger than zero, i.e. θ > 0.
 If the deposit does not wet the substrate at all, then θ =
180o, the nucleation is a homogeneous nucleation.
For layer growth, the deposit wets the substrate
completely and the contact angle equals zero.

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Nucleation of heterogeneous systems (B nucleation on A)
Liquid on a solid:
γLV
γLV γSV
θ

Young Equation:
γ LV cos θ = γ SV − γ SL
Solid on solid: γBV

γAB
γAV

Change in interface energy adding atoms of “B” to the system:

∆Ginterface ∝ γ BV − γ AV + γ AB

3 Modes of growth:
 ∆G = γ BV − γ AV + γ AB

Island or Vollmer-Weber Growth (“V-W”):

γ AV < γ BV + γ AB

Growing layer wants to minimize interface energy and its

own surface energy  Layer “balls up” on the surface
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∆G = γ BV − γ AV + γ AB

Layer or Frank- Van der Merwe Growth:

γ AV > γ BV + γ AB

Growing layer reduces : “wets” the surface

completely.
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 ∆G = γ BV − γ AV + γ AB

Stranski-Krastanov (“SK”)
Growth:
Example: Ge on Si(001)

Balance of forces changes during growth:

Typically, first layer wets surface but subsequent layers do not.
Change in balance of forces is often due to strain in the growing
layer, typically due to a mismatch in lattice constants between “A”
and “B”. 12
Nucleation Modes, cont…
The most important layer growth is the deposition of
single crystal film through either homoepitaxy, in which
the depositing film has the same crystal structure and
chemical composition as that of the substrate, or
heteroepitaxy, in which the depositing film has a close
matching crystal structure as that of the substrate.
Homoepitaxy is a simple extension of the substrate, and
thus virtually there is no interface between the substrate
and the depositing film and no nucleation process.
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Nucleation Modes, cont…
Island-layer growth is a little more complicated and
involves in situ developed stress.
 Initially, the deposition would proceed following the
mode of layer growth. When the deposit is elastically
strained due to lattice mismatch, for example, strain
energy would be developed.
 As each layer of deposit is added, more stress is developed
and so the strain energy.
 When the stress exceeds a critical point and cannot be
released, the strain energy will be large permitting nuclei
to form above the initial layered deposit.
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Sol-gel processing, cont….
Solvent Raw materials Catalyst
Heating and stirring
Sol Drying
Adding water Gel
Sintering
Precursor
Powders
Dispersing
Superfine
Mixing
Wet Substrate
Pyrolizing/Annealing
Film
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Sol-gel processing, cont…
Pros:
Simpler composition control
High reactivity
Lower synthesis temperature ± 300oC
Cons:
Influence by: alkalinity, reagents, concentration,
nature of precursors and mineralizer
Spray technique may induce crack
Screen Printing Process
Printing direction

Squeegee Screen mesh

emulsion
Paste
Frame

Substrate

Top electrode < 1 µm

Thick Film 50 µm
Bottom electrode 5 µm
Substrate 300 µm
Screen Printing Process, cont…
Pros:
Higher solid loading
Relatively shorter processing time
The ability to produce patterned structure
No need etching when patterned is needed
Cons:
Need post treatment up to 850oC
Not straightforward
Dip Coating Process
Automatic drawing

Furnace

Substrate

Solution
Dip Coating Process, cont…
Pros:
Simple process
Can be applied to large and irregular shape
Relatively low temperature process
Cons:
Influenced by the process parameter such as solution
characteristic, substrate feature, and withdrawal
speed
Laser Deposition
Mirror
Laser

Target Substrate heater

Substrate

Grid electrode

DC voltage

Plume
Rotating
Laser Deposition, cont…
Pros:
 Congruent transfer of target material
 The ability to transfer the stoichiometry of the target to
the film
 High deposition rate and relatively low processing
temperature
 Highly oriented growth of film
 In situ deposition of multilayers
Cons:
 Interfacial reaction on the substrate
Chemical Vapor Deposition
 In a CVD reactor, carrier gases, containing
the elements of the desired compound, flow
over the surface to be coated
 This surface is heated to a suitable
temperature to allow decomposition of the
carrier gas and to allow mobility of the
deposited atoms or molecules on the surface
 Mobility of deposited atoms helps to
produce a highly ordered crystalline deposit,
desired for improved electrical properties.
 In some cases laser light may be used as an
assist (LA-) in the decomposition of the
carrier gas. Processes called LACVD are used
to produce nanowires, for example.
 Molecular Beam Epitaxy (MBE)
 MBE is a process for depositing atomically perfect
(epitaxial) layers of compound semiconductors
 In MBE, separate ovens with careful temperature
regulation are provided for each element in the
desired deposit
 Temperature control is needed to control the
vapor pressure and hence the deposition rate
 The rates of each element have to precisely match
the stoichiometry. For InGaAs, e.g., there will be
three ovens.
 Deposition rate monitors and shutters will be
available for each oven. With these elaborate
precautions, in ultra high vacuum, epitaxial
layers and hetero pitaxiallayers can be deposited.
Langmuir-Blodgett Films
 LB films are monolayers and multilayers of amphiphilic
molecules transferred from the liquid-gas interface
(commonly water-air interface) onto a solid substrate.
 Certain strength of the hydrophilic head is required to
form LB films.
 If it is too weak, no LB film can be formed;
 However if it is too strong, the amphiphilic molecules is too
soluble in water to allow the formation of a monolayer.

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Langmuir-Blodgett Films, cont…
 A drop of a dilute solution of an
amphiphilic molecule in a volatile
solvent is spread on the water-air
interface.
 As the solvent evaporate, the
amphiphilic molecules are
dispersed on the interface.
 The barriers move and
compresses the molecule on the
water-air interface.
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Langmuir-Blodgett Films, cont…
 Two methods are commonly used
to transfer monolayers from the
water-air interface onto a solid
surface:
 Vertical deposition: when a substrate
is moved through the monolayer at
the interface, the monolayer can be
transferred during immersion.
 Another method is the horizontal
lifting, referred as Schaeffer’s
method, which is useful for
deposition of very rigid films.

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 Self-Assembly
Molecules will always seek the lowest energy level
available to them
 One way to imagine self-assembly is to imagine a
compass. If you shake it, you can cause the needle to
fluctuate and point in almost any direction for an
instant, but once you stop shaking it, the needle will
ultimately reorient itself and point from south to
north
 The forces involved in self-assembly are generally
weaker than the bonding forces that hold molecules
together
 In self-assembly, the nano builder introduces
particular atoms or molecules onto a surface or onto
a preconstructed nanostructure. The molecules
then align themselves into particular positions M. Ratner, D. Ratner, Nanotechnology: A Gentle Introduction to the Next Big Idea,
Prentice Hall, Courtesy of the Stupp Group, Northwestern University
Self-Assembly

AFM image of a thiol

monolayer self assembled on
gold
DIBLOCK COPOLYMER TEMPLATING OF TiO2 NANOPARTICLES
Solution preparation
Spin-coating + annealing

Micelles formation in
an appropriate solvent

Selective uptake of hydrochloric acid and titanium Structural arrangement and growth of
alkoxide into hydrophilic PEO domains (hydrolysis) arranged TiO2 nanoparticles and
and thus locally confined condensation process expectedly enhanced nanocrystallinity
PS-PEO templating PS-P2VP templating

J. Spatz, et al, Adv. Mater. 1998, 6, 10. X. Li, et al, Langmuir. 2005, 21, 5212
Z. Shun, et al, Physica A, 339, 2004, 80.
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SOLVENT MODIFICATION: EFFECT OF WATER CONTENT

(a) 10 vol % (c) 50 vol %

(b) 30 vol % (d) 60 vol %

Very acidic environment (pH
value of ~0.33) to prevent
premature agglomeration

Proportional mixture of 50
vol % water in THF leads to
the most suitable templating.
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EFFECT OF ANNEALING TEMPERATURE
(a) 60oC (b) 110oC (c) 150oC

(d) 180oC (e) 200oC

Self-assembly and nanoarray evolution as function of annealing temperature from 60 to 200 oC. 33
WATER VAPOR TREATMENT

Array Rearrangement
Of The Hexagonal-like
Steel Liner Or Cubical-like
Configurations
Teflon

Stands
Ordered
Arrangement By
Diblock
Copolymer
Templating Can
Be Maintained At
Large Scales

Hydrothermal Container
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