Intelligent Micro-Nano-Fabrication

INTELLIGENT MICRO-NANO-FABRICATION
Prof. PhD Eng. EurEng. Gh. Ion Gheorghe 1, PhD Student Iulian Ilie2, PhD Eng. Simona Istriteanu3,
PhD Eng. Valentina Bajenaru4
1
General Manager– INCD Mechatronics & Measurement Technique, Bucharest
Associated Prof. in U. Valahia of Târgovişte, U.T.M Bucharest and U. P. Bucharest
Scientific Doctorates Coordinator in Doctoral School of Mechanical Engineering, U. V. of Târgovişte
Corresponding Member of the Academy of Technical Sciences in Romania
2,3,4
INCD Mechatronics & Measurement Technique, Bucharest

Abstract:Innovations in the field of intelligent micro-nano-fabrication created unique opportunities for

micro-nano-products for micro-nano-processing on micro and nano scale micro-nano-structures. This
micro-nano-size range is applicable to new electronic, optical, magnetic, mechanical, chemical and
biological micro-nano-devices, to micro-nano-sensors, for control, etc.. Important techniques used to
manufacture micro-nano-fabrication structures occur in a range from a few microns to a few nanometers.
Important steps have been taken in the field of micro- and nano-structures by developing micro-
components of complex organic structures and micro-components of micro- and nano- polymers and
dendrimers, with high micro-mechanical and micro-optic properties by applying new advanced
technologies and an ultra-precise architecture at micro and nano level. Trends regarding these micro- and
nano-components, refer to future research for obtaining new micro- and nano-technological steps, to
address the new blocks of copolymers in molecular and atomic compositions, to address the new new
nano-crystalls for obtaining new method, semiconductors, magnets, by colloidal chemical processes and
micro-technologies and condensed matter physics. Obtaining new materials, also as a future trend, has
been driven by scientific discoveries in which the most important was the discovery of "carbon nano-
tubes", which applies in building matrices for the discovery of new materials, benefitting not only from
the construction, topology of interatomic bonds, but also from the absence of surface effects, together
with excellent electrical, optical and mechanical properties.

Keywords:micro-nano-fabrication, micro-nano-structures, micro-nano-mechatronics.,

1. Introduction techniques, genetic engineering tehniques, biological /

By approaching new micro- and nano-technologies
through a controlled process for obtaining micro-
particles, new micro- and nano-scale structures can be
obtained in various fields of materials, particularly in
ceramics, in various forms, such as clusters,
characterized by a unique morphology when it comes to
fractal dimension, single bond energy and the
coordination number.
Processing micro- and nano-structures depends mainly
on advanced developments of "auto-assembly
methodologies", that further allow the development of
"methods for obtaining micro- and nano-structures."
In this respect, micro- and nano-structure design is
based on the application and implementation of micro-
and nano-technologies for obtaining micro-lithography
templates and samples meant to develop new methods
and ways of producing, assembling and binding macro-
molecules and nano-objects.
The discovery of new bio-compatible micro- and nano-
materials, with very sophisticated properties, depends
more and more on their synthesis by new approaches,
type"bottom-top", borrowing a lot of supra-molecular
chemistry techniques, colloidal techniques, soil-gel
molecular bio-chemistry techniques, overlapping the
new methods of manipulation and synthesis with laser
beams, etc..
The evolution of intelligent mechatronic nano-
processing micro-systems or intelligent mechatronic
micro-systems with nanometric and sub-nanometric
precision has seen spectacular shifts, as the new
principles of micro- and nano-processing, the new
principles of micro- and nano-constructive solutions, the
new smart materials with superior (physical, chemical,
mechanical, tribological, etc..) properties and the new
approaches for micro- and nano-sized products were
discovered.
The evolution of intelligent mechatronic nano-
processing or processing micro-systems has also
experienced dramatic shifts in terms of the accuracy of
nano-processing, leading to precision and accuracy
below 1 nm.
Research work from all over the world have adressed
the new micro- and nano-technology that have lead to
new mechatronic intelligent technological micro-
systems appropriate for the new current requirements,
such as the minimization of systematic and random , the
optimization of the process capability index and the

The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46 71
 Intelligent Micro-Nano-Fabrication

systematization of nano-technology. properties of matter, at nanoscale.

Of this research work from all the world, we highlight These include important quantum mechanical
the following: phenomena (such as conductance quantification and
 intelligent mechatronic micro-systems for Coulomb blockade) arising from the limitation of
processing silicon plates; electrical charge transporters in structures, quantum
 intelligent mechatronic micro-systems for dots, fig. 1.
integrated circuits assembly--processing; From a practical perspective, the use of nano-structures
 intelligent mechatronic micro-systems for in electronics / optics and sensors can lead to significant
corrosion in dry process and wet process; improvements in performance.
 intelligent mechatronic micro-systems for mask In the field of devices, the investigators relied on
processing; manufacturing nanometer-sized transistors, in
 intelligent mechatronic micro-systems for disc anticipation of the technical difficulties provided by
printing; Moore's Law for a resolution of more than 100 nm.
 etc. In addition, optical sources and detectors with
As a further evolution, intelligent mechatronic nano- nano-sized dimensions have improved features that are
processing or processing micro-systems will head to not achievable in larger devices (lower threshold
higher atom by atom processing nano-technologies. powers, improved dynamic behavior and improved
8.2 Micro-nano-technologies for intelligent wavelenght of line emission in quantum dots lasers).
manufacturing These improvements create major opportunities for the
Micro-nano-fabrication µnmechatronic techniques are next generation of communication and computing
adapted for the fabrication of mechatronic devices devices. In the field of sensorics, the decrease in size
within the range of 1 µm - 1 nhm. beyond conventional optical litography can provide an
Nano-structures provide a tool for studying the improved sensitivity and selectivity.
electrical, magnetic, optical, thermal and mechanical

Fig. 1. Important quantum structures:

a) quantum cavity, b) wire, c) quantum dots.

The various mechatronic nano-fabrication micro-processing.

techniques nanofabricare mechatronic techniques can be
divided into top-down and buttom-up teniques. The
first approach starts with a thin film or bulk material
which removes selective regions in order to
manufacture nano-structures (similar to micro-
processing techniques). The second method is based on
molecular recognition and self-assembly and used to
manufacture nano-structures from smaller pieces
(molecules, colloids and groups). The top-down
approach is a branch of standard lithography techniques
The bottom-up approach, on the other hand, is
more strongly influenced by chemical engineering and
materials science and is based on fundamentally
different principles. Therefore, five major mechatronic
nano-fabrication techniques will be presented,
including: i) fabrication with electron beam and nano-
print ii) force engineering and epitaxy iii) mechatronic
sample scanning techniques iv) self-assembly and
template fabrication; v) chemical techniques for the
fabrication of nano-particles and nano-wires.

72 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
 Intelligent Micro-Nano-Fabrication
2.μnFabrication with electron beam and nano-print
There are various important litography techniques
used in micro-nano-fabrication and MEMS. These
include various forms of UV lithography (normal, active
and extreme) and X-ray.
Due to the lack of resolution (for UV) or
difficulties in mask making and sources of radiation (X
rays), these techniques are not suitable for nano-scale
fabrication.
Electron ray lithography is an attractive
alternative technique for making nanostructures. It uses
an electron beam to expose an electron-sensitive coating
layer such as polimetilmetacrilate (PMMA), dissolved
in trichlorobenzene (positive) or policlorometilstirene
(negative).
The electron beam gun is usually part of a
scanning electronic microscope (SEM), but transmission
electron microscopes can also be used. While Ȧ
wavelengths are easily reached, electron scattering in
the protective layer limits the resolution that can be
achieved to > 10 nm.
Beam control and template generation is done
through a computer interface. Electron beam
lithography is serial and therefore has poor results.
Although this is not a major concern when
manufacturing devices used in the study of fundamental
micro-physics, it severely limits nano-fabrication on a
Fig. 2. Nano-imprint manufacturing scheme
The coating used in nanoimprint technology can
be thermoplastic, a UV-curable polymer, or a heat
resistant polymer.
For a thermoplastic coating (such as PMMA),
the substrate is heated more than the glass transition
temperature (T g) of the polymer before stamping and it
The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
large scale.
Electron beam lithography, in connection with the
lifting, etching and electro-deposition processes can be
used for obtaining various nano-structures.
A new interesting mechatronic technique that
fights back the serial and small limitations electron
beam lithography for manufacturing nanostructures is
known as nanoimprint technology.
This technique uses a stamp (template) made up of
a strong material and manufactured using electron
beams to punch and deform a polymer protective layer
(coating). This is usually followed by a reactive ion
etching phase meant to transfer the template to the
substrate.
This technique is superior economically as a
single stamp can be used repeatedly to manufacture a
large number of nano-structures.
Figure 2 shows a scheme of nano-imprint
manufacturing. First, a stamp from a hard material (like
silicon or SiO 2) is created using electron beam
lithography and etching with reactive ion.
Then, a substrate coated with a protective layer is
stamped and, finally, an anisotropic RIE (reactive ion
etching) is performed to remove the residues from the
protective layer, in the stamped area.
At this point, the process is complete and the substrate
can be stamped or, if metal structures are used, the
metal evaporates and the lifting is done.
is cooled below T g before the stamp is removed.
Similarly, UV and heat resistant coatings are
completely cleaned before the stamp is separated.
The available resolution in nano-imprint
technology is limited by the strength of both the powder
and the polymer, and may be of 10 nm.
73
 Intelligent Micro-Nano-Fabrication
A nanoimprint technique recently used for
stamping a silicon substrate in less than 250 ns using
XeCl laser (308 nm) and a quartz mask (LADI - laser
assisted direct imprint), fig. 3.
Fig.3. Very fast silicon nano-print using a XeCl laser
Figure 4 shows the SEM micro-diagrames of the
quartz print and the silicon substrate printed with lines
of 140 nm obtained using LADI. Nano-print
lithography processes were also modified for nano-fluid
channel fabrication (for manipulating DNA) and
multilayer polymer structures.
Figure 5 shows a cross section of nano-fluidic channels
fabricated using imprint lithography.
Fig.4. a, b. SEM Micro-diagrames of:
a. a quartz template and b) a silicon surface
printed using LADI
Fig.5 Solar rays of a nano-fluidic channel using nano-
imprint lithography
74 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
3. μnFabrication quantum structure using epitaxis
on moulded substrates
Precise atomic deposition techniques like
molecular beam epitaxy (MBE) and chemical deposition
of metal-organic vapours (MOCVD) have proven to be
useful means for the fabrication of confined quantum
structures and devices (including quantum source lasers,
photodetectors and resonant unnel diode). Although
quantum sources and super-structures are structures that
are the most suitable for these techniques (Fig. 1a),
quantum wires and quantum dots were also made by
adding additional steps such as etching or selective
growth. Quantum cavity and super-structures
fabrication using epitaxial growth is a mature and well
developed field.
Various ways were used to manufacture wires and
quantum dots using epitaxial layers. The simplest
method involves electron ray lithography and etching a
epitaxially grown layer (such as InGaAs on a GaAs
substrate).
Due to damages and / or contamination occurring
during lithography, this method is very suitable for the
active fabrication of the device (of lasers with quantum
dots, for example).
Various other methods involving epitaxial layers
growth over uneaven surfaces as side-stair, split-ende
and shaped substrate were used to fabricate quantum
wires and dots without the need for the lithography and
etching of the quantum structure.
These templates of the uneaven surace can be
produced in a variety of ways, such as etching through a
mask or split along the crystallographic planes.
Subsequent epitaxial growth on top of these
structures results in a set of planes with different growth
rates depending on the geometry or surface diffusion
and adsorption effects. These effects can increase or
limit the growth rate in various planes, resulting in
shaping and limiting of lateral epitaxial layers deposited
and the formation of quantum wires (in channel V) and
dots (in inverted pyramids).
Figure 6 shows a schematic section of an InGaAs
quantum wiresfabricated in a V channel of InP. As can
be seen, the growth rate on the sidewalls is less than in
the surfaces from the top and the bottom.
Therefore, a thinner InGaAs layer from the basis
of the V channel forms a quantum wire limited at the
edges with a thinner layer with a larger gap between the
bands.
Figure 7 shows a quantum wire formed using
epitaxial growth over a dielectric planar shaped
substrate. Quantum cavity creation isnrelatively eassy
using any of these techniques; however, in order to
create wires and quantum dots, electron beam
lithography is still necessary to mold channels and
window templates.
 Intelligent Micro-Nano-Fabrication
Fig. 6. (A) Fabricated InGaAs Quantum Wires in a V
channel of InP and
(B) AlGaAs quantum wire fabricated by epitaxial
growth on a masked GaAs substrate
4. Quantum structure μnfabrication using self-
assembly induced by bending
A more recent mechatronic technique for
manufacturing quantum wires and dots involoves self-
assembly induced by bending. „Self-assembly” is a
process where a 2D curved system decreases in energy
by changing a 3D morphology. The combination of
materials most commonly used in this technique is the
In x Ga 1-x As / GaAs system, which offers a large
network mismatch (7.2% between InAs and GaAs),
although the Ge dots on the Si substrate have attracted
attention recently. This method is based on network
mismatch between the epitaxial layer and its substrate,
resulting in the formation of a multitude of quantum
dots and wires. Figure 8 shows a scheme of self-
assembly process induced by bending. When the
network constants of the substrate and the constants of
the epitaxial layer are markedly different, only the first
few monolayers deposited epitaxially crystallizes in
curved layers in which network constants are equal.
When a critical thickness is reached, a
significant bending occurs in the layer, resulting in
breaking the spontaneous formation of ordered
structures and spontaneously distributed islands with
regular shapes and similar sizes. This growth is usually
known as Stranski-Krastanow mode.
The size, separation and height of the quantum
dot depends on deposition parameters (total amount of
material deposited, growth rate and temperature) and the
combinations of materials.
As one can see, this is a very convenient method
to grow perfect crystalline nanostructures over a large
area without lithography or etching. A major drawback
of this technique is the random distribution of quantum
dots. This technique can also be used in the fabrication
of quantum wires by relaxing the bending at the ends of
the phase.
The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
Fig. 7. Stranski-Krastanow growth method,
(A) 2D wett layer, (b) increasing the raw side and
breaking, (C) coherent 3D self-assembly
5. Sample scanningμntechniques
The invention of sample scanning microscopy
(SPM) was a revolution in imaging and spectroscopy at
atomic scale. In particular, scanning tunneling
microscopes (scanning through tunneling) and atomic
force microscopes (STM and AFM) have applications in
physics, chemistry, materials science and biology. The
ability to perform atomic-scale manipulation,
lithography and nano-processing using such probes has
been considered from the beginning and has evolved
considerably in the last decade.
Sample scanning microscopy systems involve
the controlof the movement of an atomic sharp tip near
or in contact with a surface with sub-nanometer
accuracy. Piezoelectric positioning systems are usually
used to achieve such precision. High resolution images
can be obtained by scanning tips over a surface, while
monitoring the tip-surface interaction.
In tunnelling scanning microscopic systems, a
polarized voltage is applied to the sample and the tip is
positioned close enough to the surface for a tunneling
current to develop across the hole (Fig. 8a).
Because this current is sensitive to the distance
between the tip and the surface, scanning the tip in the
xy plane while recording the tunneling current allows
drafting surface topography with atomic scale
resolution.
In a more common operation, an amplified
current signal is connected to the piezoelectric
positioning system on the z-axis by a reverse loop
connection, so that the current and the distance are kept
constant during scanning. In this configuration, the
surface topography image is obtained by recording the
vertical position of the tip in each xy position.
The STM works only for conductive surfaces
and establishes a tunneling current. Atomic force
microscopy, on the other hand, provides a conductive
surface observation and conducting.
75
 Intelligent Micro-Nano-Fabrication

In AFM, the tip is attached to a cantilever is

flexible and brought into contact with the surface (Fig.
9b).
The force between the tip and thesurface is
detected by sensing the beam deflection in the console.
A topographic image is obtained by plotting the surface
deviation as a function of the x-y position.
In a more common operation, a loop with reverse
connection is used to maintain a constant deflection
while topographic information is obtained by moving
vertically the beam in console.
Some sample-scanning systems use a combination
of the AFM and STM modes: the tip is mounted in a
beam with a console with an electrical connection so
that the surface force and tunneling current are
controlled or monitored.
STM systems can be functional in ultra-high
vacuum (UHV STM) or in the air, while AFM systems
are only operational in the air.
When a sample scanning system is operational in
the air, the water absorbed on the surface of the sample Fig. 9. SEM image of a reverse truncated pyramid
accumulates under the tip, forming a meniscus between surface fabricated on a SOI silicon capsule by SPM
the tip and the surface. The water meniscus plays an oxidation and subsequent etching in TMAH (lift is of
important role in some of the sample scanning 500 nm)
techniques described below.
It is assumed that the water meniscus formed at
the point of contact serves as electrolyte so that the tip
polarized oxidizes a small surface area such as an
anode.
The most common application of this principle
is inactivated silicon oxidation with hydrogen.
To inactivate the surface of silicon with
hydrogen atoms, it is often dipped in HF solution.
Oxide templates "written" on a silicon surface can be
used as a mask in wet and dry etching.
Templates with line diameters of 10 nm were
successfully transferred on a silicon substrate in this
way. Different metals were also anodized locally
(aluminum or titanium, for example) using this method.
An interesting variation of this process is
deposited amorphous silicon anodization. Amorphous
silicon can be deposited at low temperatures on a
variety of materials.
The deposited silicon layer can be modeled and
can be used as, for example, a 0.1 mm CMOS transistor
gate or can be used as a mask to shape a support film.
The biggest drawback of this technique is poor
reproducibility due to tip wear during anodization.
However, the application of AFMs in non-contact mode
Fig. 8. a, b sample scanning systems: (a) STM and (b)
has helped to overcome this problem.
AFM
 Protective layer exposure to scanning and
litography
 Oxidation induced by scanning the sample
Electrons emitted from a polarized SPM tip can be
Nano-scale local oxidation of various materials can be
used to expose a protective layer in a manner similar to
achieved using air samples and functional scanned
electron beam lithography (Fig. 10).
samples and polarized at a high enough voltage, fig. 9.
Various systems were used in this lithographic
Polarizations of -2 to-10V are normally used, with
technique, including constant-current STM systems,
writing speeds of 0.1 - 100 mm / s in an ambient
AFM and non-contact AFM systems with constant tip-
humidity of 20% - 40%.
protective layer force and constant current.

76 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
 Intelligent Micro-Nano-Fabrication
Systems using beams in console have the
advantage that AFM observation and alignment can be
achieved without exposing the protective layer.
Coatings that are well characterized for electron beam
lithography (as PMMA or SAL601) lithography were
used to scan the sample for accurate lithography below
100 nm.
The procedure for this process is as follows. The
capsules are cleaned and the native oxide (silicon or
poly) is removed with HF dipping.
A coating with a thickness of 35-100 nm is then
deposited on the surface.
Exposure is achieved by moving the SPM tip over the
surface while applying a polarized voltage that is large
enough to produce the emission of electrons from the
top (a few tens of volts).
The protective layer is developed in a standard solution
subsequent to exposure. Features with a thickness of
more than 50 nm were obtained with this procedure.
Fig. 10. Sample scan lithography with a protective
organic coating
 Dip-pen lithography (litography by dipping the tip)
In dip-pen nano-lithography (DPN) a functional
AFM tip is "stained with ink" with a certain chemical
and brought in contact with a surface. The molecules of
ink flow from the tip to the surface as a in a pen. The
water meniscus formed between tip and the surface
allows a natural diffusion and transport of molecules, as
shown in Fig. 11.
Fig. 11. Scheme of the operating principle of dip-pen
nano-litography
The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
Ink staining can be done by dipping the tip in a
solution containing a small concentration of molecules
followed by a drying step (difluoroetane drying, for
example). Lines with widths of up to 12 nm and spatial
resolution of 5 nm have been demonstrated with this
technique. Samples shaped with DPN include
conducting polymers, gold, dendrimer, DNA, organic
dyes, antibodies and alcanitiolsi. Alcantiols were used
as an organic etching mask in a gold monolayer and
then in the engraving of the exposed silicon substrate.
The beam in cantilever of the AFM can also be used to
control the deposition of solid organic ink. This
technique was recently reported by Sheehan and his
colleagues, where 100 nm lines of octadecilfosforic
acid (melting point 100 ° C) were written using a
sample AFM head.
 Other techniques nanofabricare by scanning the
sample
A variety of mechatronic nano-fabrication
techniques based on sample scanning systems were
demonstrated. Some of these demonstrations prove the
concept and must be assessed as viable and repeatable
manufacturing processes.
For example, a substrate can be machined using
STM / AFM tips operating as planes or engraving
devices. They can be used directly to create structures
in the substrate, although it is more convenient to use
them to shape a protective layer for the subsequent
etching, an elimination or electrodeposition phase.
Mechanical Nano-processing of SPM samples
can be facilitated by heating the tip for glass transition
for a polymer substrate. This circumstance was applied
to data storage systems based on SPMs in polycarbonate
substrates.
Electric fields strong enough to induce atomic
emission from the tip can be easily generated by
applying voltage pulses greater than 3V. This strategy
was used to transfer material from the tip to the surface
and vice-versa. Ten to twenty nanoscale stacks of
metals as Au, Ag and Pt were deposited on a surface or
moved on a surface in this way.
The same path was used to extract single atoms
from the surface of the semiconductor and re-deposit
them elsewhere. Manipulation of nanoparticles,
molecules and atoms on a surface alone was also
achieved by simply pushing or sliding them with the
SPM tip. Metals can also be locally deposited using the
STM chemical vapor submission technique.
In this technique, an organo-metallic precursor
gas is introduced into the STM chamber. A voltage
pulse is applied between the tip and thesurface
dissociates the precursor gas in a thin layer of metal.
Local electrochemical etching and
electrodeposition are also possible using SPM systems.
A drop of the appropriate solution is placed on the
substrate. Then the STM tip is immersed in the drop
and a voltage is applied. To reduce Faradic currents, the
tip is coated with wax so that only the tip is exposed to
the solution. Characteristic sizes below 100 nm were
77
 Intelligent Micro-Nano-Fabrication
obtained with this technique.
Using a single peak to produce in series the
desired changes in one area leads to very slow
manufacturing processes that are not practical for mass
production.
Many of the techniques developed so far for
scanning the sample, however, could also be reploaced
by an area of peaks, which would increase their result
and would make them more competitive with other
nano-fabrication processes. This way has been
demonstrated for observation, lithography and data
storage using both uni-dimensional areas and bi-
dimensional areas of scanned samples. With the
development of larger areas, with individual advances in
force, vertical position and current control, many of
these techniques can be used in standard industrial
manufacturing.
6. Self-assembly and template fabrication
Self-assembly is a nano-fabrication technique
involving nanoparticle colloidal aggregation in the
desired final structure. This aggregation can be
spontaneous (entropic) and due to minimum
thermodynamic value constraints (minimizing energy)
or due to the chemical and complementary binding of
organic molecules and supra-moleculels (molecular
self-assembly). Molecular self-assembly is one of the
most important techniques used to develop complex
functional structures in biology.
Since these techniques require that the target
structures are thermodynamically stable, it is going to
produce structures that are free from defects and self-
healing. Self-assembly is by no means limited to
molecules or nano scale and can be performed at any
scale, as a strong (multi-ordination) manufacturing
method.
Another attractive feature of this technique
refers to the possibility of combining self-assembly
properties of organic molecules with electronic,
magnetic and photonic properties of inorganic
components. The fabrication of the basic template is
another technique that uses top-bottom deposition (CVD
electroplating, and others) in nano-templates to
manufacture nanostructures. The nano-templates used
in this technique are usually prepared using self-
assembly techniques.
The following sections will discuss various
techniques of self-assembly and production of templates
investigated intensively.
 Physical and chemical self assembly
The central theme behind the self-assembly process is
the spontaneous (physical) or chemical aggregationof
colloidal nanoparticles. Spontaneous self-assembly
exploits the tendency of sub-micro-colloidal nano-or
mono-dispersate spheres to self-organize in a network
with acentered cubic facade (FCC). The force that
generates this process is the urge to achieve a
thermodynamically stable state (minimum free energy)
78 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
of the system. In addition to spontaneous thermal self-
assembly, gravitational forces, convection and electro-
hydro-dynamic forces can also be used to induce
aggregation in complex 3D structures. Chemical self-
assembly requires the attachment of a single organic
molecular layer (monolayer self-assembled or SAM) of
(organic or inorganic) colloidal particles and subsequent
self-assembly of these components in a complex
structure using molecular recognition and binding.
 Physical self-assembly
This is a method based on the entropy driven by
the spontaneous organization of colloidal particles in a
relatively stable structure through non-covalent
interactions. For example, polystyrene colloidal spheres
can be assembled into a 3D structure on a substrate that
is held vertically in the colloidal solution, Fig. 12.
After evaporation of the solvent, the spheres aggregate
in a hexagonal closely packed (HCP) structure. The
interstitial pore size and density are determined by the
size of the polymer sphere. Polymer spheres can be
engraved in smaller sizes after the formation of HCP
surfaces, thereby altering pore printing separations.
This technique can produce large areas modeled
in a fast, simple and economic manner. A classic
example is the assembly of on-chip natural silicon
photonic crystals that are capable to reflect the incoming
light in any direction over a certain wavelength domain.
In this method, a thin layer of colloidal silica spheres
are assembled on a silicon substrate. This is done by
placing a vertical silicon capsule in a vial containing an
ethanolic suspension of silica spheres.
A temperature gradient over the vial helps pick
up the silica spheres. Figure 13 shows a cross-sectional
SEM image of an oval flat thin template assembled
directly on the silicon capsule of the 855 nm spheres.
Once such a template is prepared, LPCVD can be used
to fill the interstitial spaces with silicon, so that high
refractive index silicon zones provide the necessary
width.
Fig. 12. Self-assembly of colloidal particles on solid
substrates
after drying in a vertical position.
 Intelligent Micro-Nano-Fabrication
Fig. 13. SEM image of a cross section of an oval flat
thin template
(spheres with a 855 nm diameter) assembled
directly on a silicon capsule.
You can also store colloidal particles on a
shaped substrate (template-assisted self-assembly). This
method is based on the principle that when an aqueous
dispersion of colloidal particles is let to dehydrate on a
solid surface which is already modeled, colloidal
particles are blocked by deep regions and assembled in
aggregates of shapes and sizes determined by the
geometrical limitation provided the template. Templates
modeled surfaces can be manufactured using
conventional photo-lithography to ensure the control of
the shapes and sizes of templates, thus allowing the
assembly of complex structures of colloidal particles. A
cross section of a fluidic cell used in TASA is shown in
Figure 14.
Fig. 14. Cross section view of a fluidic cell
used for template-assisted self-assembly
The fluidic cell has two parallel glass substrates
to limit the aqueous dispersion of the colloidal particles.
The surface from the basis of the substrate is modeled
with a 2D templates surface.
The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
When the aqueous dispersion is let to dehydrate
slowly across the cell, the capillary force exerted over
the liquid pushes the colloidal spheres across the surface
of the basic subsatre until they are blocked by the
template.
If the concentration of colloidal dispersion is
sufficiently high, the template will be filled with the
maximum number of colloidal particles determined by
the geometric limit. This method can be used to
manufacture a variety of polygonal and polyhedral
aggregates that are otherwise difficult to generate.
 Chemical self-assembly
Organic and super-molecular SAM plays a
critical role in the self-assembly of colloidal particles.
SAMs are organic molecules that are absorbed
chemically by robust solid substrates. They often have
a hydrophilic head (polar), which can be linked to
various solid surfaces and a long hydrophobic
(nonpolar) tail that lies outside. SAMs are formed by
immersing a substrate in a diluted solution of the
molecule in an organic solvent. The resulting film is a
dense organization of molecules arranged to expose the
final group.
SAM sustainability is strongly dependent on the
strenght of anchoring to the surface of the substrate.
SAMs have been studied intensively since the end group
can be functionalized to form molecular surfaces
arranged specifically for applications ranging from
simple insulators and plain lubricants to biological
sensors. SAMs use chemical self-assembly or
supramolecular organic binding and recognition as areas
for the fabrication of complex 3D colloidal
nanoparticles. The most common organic monolayers
used include: 1) organosiliconate compounds on glass
surfaces and silicon oxide layers, 2) alcantiolsi, Dialkyl
disulfide and gold Dialkyl sulfide, 3) fatty acids on
aluminum oxide and other metal oxides and 4) DNA.
Octadeciltriclorosilane (OTS) is the most
commonly used to form SAM organosilane mainly
because it is not heavy and forms dense layers.
Alchiltriclorosilane monolayers can be prepared on
silica capsules with silicon oxide surface (SiOH groups
with nearly 5.10 14 / cm 2). Fig. 15 shows a schematic
representation of the formation of monolayers by
adsorption of alchiltriclorosilan solution on substrates of
Si / SiO 2. Since the silicon-chlorine contact is
susceptible to hydrolysis, the amount of water in the
system must be limited to obtain monolayers of good
quality.
Monolayers made of methyl-and vinyl-
alchilsilanes are autophobic in hydrocarbon solution and
thus appear wet in the solution used for their formation.
The disadvantage of this method is the fact that
a cloudy film is deposited on the surface (due to the
formation of a polymer gel in siloxane) if the
alchiltriclorosilane in the solvent adherent to the
substrate is exposed to water.
79
 Intelligent Micro-Nano-Fabrication
Fig. 15. (A) Alchilsiloxane made from the adsorbtion
of alchitriclorosilanei formed on the Si / SiO 2
substrates. (B) Schematic representation of the process
Alcantioli (X (CH 2) n SH, where x is the final group) on
gold form another important group of organic SAM
systems. A major advantage of using gold as the
substrate material is that it does not have a stable oxide
and can thus be operated in ambient conditions.
When a fresh, clean, hydrophilic gold substrate is
immersed (for a few minutes to several hours) in a
dilute (10 -3 M) of organic sulfur compounds (alcantioli)
in a solvent inorganic monolayers oriented, well-packed
can be obtained.
Sulfur is used as group head due to strong interaction
with the gold substrate (44 kcal / mol), resulting in the
formation of an ordered monolayer, well packaged. The
final grouping of alcantioli can be changed to show
hydrophobic or hydrophilic properties to the adsorbed
layer.
Another method for SAM alcantioli deposition is soft
lithography. This technique is based on staining an
alcantiol PDMS template with ink and then transfering
it to planar and non-planar substrates. Alcantiol
functionalized surfaces (planar, non-planar, spherical)
can also be used to self-assemble a variety of complex
3D structures.
Carboxylic acid derivatives self-assemble on surfaces
(like glass, Al 2 O 3 and Ag 2 O) by acid-base reaction,
giving rise to fatty acid monolayers.
The time required to form a complete monolayer
increases with decreasing concentration. Higher
concentrations of carboxylic acids are necessary to form
a monolayer on gold rather than on Al 2 O 3. This is due
to different affinities of these substances of the COOH
group (higher affinity for Al 2 O 3 and glass than gold)
and also the concentrations of surface oxides that are
salt makers in the two substances. In the case of
amorphous metal oxide surfaces, the chemical
adsorbtion of alcanoic acids is not unique. For example,
on Ag 2 O, the two atoms of carboxylic oxygen
substrate binds in a nearly symmetrical bond, resulting
80 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
in ordered monolayers with a chain tilt angle of 15 º to
25 º. However, on CuO and Al 2 O 3 , oxygen atoms
bind symmetrically and chain angle is close to 0 °.
The structure of monolayers is thus the result of a
balance between various interactions that occur between
polymer chains.
The deoxyribonucleic acid (DNA) – the skeleton on
which all life is built - can be used in self-assemble
nano-materials into macroscopic aggregates that show a
number of useful physical properties desired. DNA
consists of two chains that are wrapped around one
another to form a double helix. Single chains of
nucelotides are left when the two chains are wrapped.
These nucleotides are composed of a sugar (pentose
ring), a phosphate (PO 4) and a nitrogen base.
The right order and the architecture of these
components are essential for achieving a proper
structure of nucleotides. Four nucleotides form usually
the DNA, adenine (A), guanine (G), cytosine (C) and
thymine (T). A basic property of the structure of DNA
nucleotides describes is that they bind specifically to a
different nucleotide in the double helix when they self-
assembly (A binds to T and C bins to G).
This specific binding capability can be used to
assemble the material in nano-phase and nano-
structures. For example, nucleotides functionalized
with gold nanoparticles were assembled in complex 3D
structures by attaching DNA chain to gold through a
binding molecule or a bond. In another work, the DNA
was used to assemble nano-particles inmacroscopic
materials.
This method uses alkane ditiol as biding molecule to
connect the DNA to the nano-particule. Thiol groups at
each end of the molecule are attached covalently to the
colloidal particles to form aggregate structures.
 Template fabrication
Template fabrication refers to a set of techniques that
can be used in the fabrication of organic and inorganic
3D structures from a nano-template. These templates
differ in material, template, sizes, features, full size
template and regularity.
Although nano-templates can be manufactured using
electron beam lithography, the serial nature of this
technique prohibits its application. Self-assembly is the
preferred technique since it can produce high surface
nano-templates. A series of nano-templates were
investigated for use in the fabrication of templates.
These include colloidal polymer spheres, aluminum
membranes and nuclear membranes with engraving
traces. Colloidal spheres can be deposited on a regular
3D surface using the techniques described above.
Aluminum oxide porous membranes can be produced
by anodic oxidation of aluminum. The oxidized film
consists of coloumnar surfaces from hexagonal pores
separated by distances comparable with pore size. By
controlling the electrolyte species, temperature, voltage
and time, pores wkith sizes, densities and heights can be
obtained.
 Intelligent Micro-Nano-Fabrication
Pore size and depth can be adjusted by a proper
acid corrosion. Porous polycarbonate templates or
membranes can be fabricated by etching traces of
nuclear membranes. This technique is based on the
transfer of high energy fragments from a radioactive
source to a dielectric material. Particles leave behind
traces which can then be chemically active and can
create corroded pores through the membrane. Pores
separation and thus pore density is thus depending on
pore size. The pore density is determined only by the
irradiation.
After the fabrication of the template, the
interstitial spaces (in colloidal spheres) or pores (in
aluminum oxide and polycarbonate membranes) in the
template are filled with the desired material. This can
be done using a variety of deposition techniques, like
electroplating and CVD. The final structure may be a
composite of the nano-template and of the dmaterial, or
the template can be selectively etched resulting in a
complex 3D structure filled with air. For example,
nickel, iron and cobalt nano-wires were grown
electrochemically in a porous mould. Three-
dimensional photonic crystals were fabricated by
electrochemical depositing of CdSe and silicon in
polystyrene and colloidal assemblies of silicon oxide.
An interesting example is the synthesis of metallic
barcode with nanometric dimensions.
These nano-barcodes are prepared by the
electrochemical reduction of metal ions in the pores of
the aluminum oxide membrane followed by their release
by etching the templates. This procedure is illustrated
schematically in Figure 16.
Fig. 16. Barcode particles synthesis parciculelor
A film of silver on the back is used as the
working electrode to reduce the metal ions (silver and
gold in this case) of the solution. Over seven different
metal segments of 10 nm and several micrometers long,
with 13 strips, can be distinguished using this technique.
Optical reflectivity is used to read the template encoded
in the metalic particles.
Figure 17 shows optical microscope images and
electron emission scanning microscope images of a
The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46
multi-band Au-Ag bar code (Ag strips with lengths of
60-240 nm that are separated by segments of 550 nm
can be seen). These encoded fnano-particles can be
used in luorescent surfaces and surfaces based on mass
spectroscopy, allowing a wide variety of bio-analytic
measures.
Fig. 17. Multi-band Au-Ag particle images (a) Optical
and (b) FE-SEM
In conclusion, various techniques for micro /
nano-fabrication used for fabrication of structures
covering a wide variety of sizes (mm-nm) were
presented. Starting with some of the most common
micro-fabrication techniques (lithography, deposition
and etching), a sum of micro-processor technologies and
MEMS that can be used to manufacture microstructures
up to ≈ 1μm were presented. These techniques have
reached an adequate level of maturity that allows the
production of commercial products based on MEMS
(pressure sensors, accelerometers, gyroscopes, etc.).
More recently, nano-sized structures have attracted
much interest due to their electrical, magnetic, optical,
thermal and mechanical properties. This could lead to a
variety of electronic, photonic and detection devices
with superior performance compared to macro devices.
Nano-fabrication techniques were presented. Thus,
electron beam lithography and other lithography types
with high resolution can be used to produce nanometer-
scale structures. Other potential techniques are self-
assembly and nano-print lithography. Of these, self-
assembly is the most promising due to its low cost and
the ability to produce nano-structures at different length
scales.
6.Foundation and future of intelligent micro-nano-
fabrication
The substantiation of intelligent micro-nano-
fabrication in the future is based on the new generative
techniques and technologies at micro and nano-scale,
together with the prediction of the implications of the
new discoveries of the fields but also of the products
and technologies in the micro-nano area.
The new advanced areas in which the intelligent
advanced micro-nano-fabrications will be implemented
are still listed and identified as follows:
The concept of "nanotechnology" provides its
applications in its advanced generation and evolution in
the following areas:
81
 Intelligent Micro-Nano-Fabrication

 in the field of biological systems for membranes, in the field of of aerogels;

enzymes and other cellular generated components;  in the field of intelligent uniforms made from
 in the field of carbon structures (eg nano-structures); materials improved with polymers;
 in the field of silicon structures and other enzymatic  in the field of "computer- clothes" ;
substances fabrication;  in the field of intelligent clothes realization meant to
 in the field of nano-materials and nano-semi- prevent aging, made from the new "NanoDew" material.
conductors fabrication;
 in the field of the production of nano-computers; References:
 in the field of artificial intelligence approaching;
 in the field of the production of MEMS AND NEMS; [1] Albrecht, A. et. al., “Mikrobewegungssysteme”,
● in the field of BIOMEMS AND BIONEMS;
Mikroelectronik, 1993 (5), Fachbeilage
“Mikrosystemtechnik”
 in the field of the realization of bio-sensors / bio-
[2] Altrock, K., “Signalverarbeitung fur
micro-sensors/ bio-nano-sensori;
Sensorsysteme”, Mikroelectronik, 1993 (3),
 in in the field of micro-nano-devices that achieve
Fachbeilage “Mikrosystemtechnik”
high-speed and are characterized by great flexibility;
[3] Brugger, J. et al., Microfabricated tools for
 in the field of diamond tubes production; nanoscience, Jour-nal of Micromechanics and Microen-
 in the field of "assemblers" for new materials with gineering, 1993 (4), Vol. 3
micro-structures; [4] Brugger, J. et al., “Nanopositioniersystem”,
 in the field of "re-producers" for finished products, Mikroelektronik, 1993 (5), Fachbeilage
such as micro-nano-machines; “Mikrosystemtechnik”
 in the field of nano-sized "nano-computers"; [5] Buker, H., “Glasfasersensorik als neue Disziplin der
 in the field of block co-polymers; Mikrosensorik”, 7. IAR Kolloquium, Tagungs-band,
 in the field of nano-crystals; Universitat Duisburg, 1993
 in the field of the production of clusters of [6] Burns, V. , “Mikroelectromechanical Systems
nanoparticles; (MEMS) and SPC Market Study” mst news.

82 The Romanian Review Precision Mechanics, Optics & Mechatronics, 2014, No. 46