Module 4

Organic Thin Film Growth

 Thin Film
A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to
several micrometers in thickness. The controlled synthesis of materials as thin films (a
process referred to as deposition) is a fundamental step in many applications.

A familiar example is the household mirror, which typically has a thin metal coating on
the back of a sheet of glass to form a reflective interface.
History
Classification of Thin films on the basis of Crystalline Structure

Single crystals
Epitaxial
Polycrystalline
Amorphous
Thin film growth Process
• As the name suggests, PVD is a technique that uses primarily
physical means to deposit a thin layer of material. PVD involves
a number of steps performed under high-temperature vacuum
conditions. First, a solid precursor material is gasified, typically
through the use of high-power electricity or laser. The gasified
atoms are then moved into a reacting chamber where the
coating substrate is located. Source material atoms then stick to
the substrate, forming a thin coat.
• PVD is used as the deposition method to produce an extremely
hard, corrosion-resistant coating. Thin films made with PVD have
a high-temperature tolerance and superior ablation resistance.
PVD is also considered an environmentally-friendly process.
• The process does have a few drawbacks. One of the main
drawbacks is its high cost, due in part to the intense heating and
cooling that is required. PVD is also a ‘line of sight’ technique,
which means it is not ideal for coating non-visible surfaces. The
process is also considered to be relatively slow.
 Chemical vapour deposition
The main steps that occur in a typical CVD process can be summarized as The main CVD process parameters—such
follows: as temperature, pressure, reactant gas
(1) transport of reacting gaseous species to the surface of a substrate, concentration, and total gas flow—require
(2) adsorption of the species on that surface, accurate control and monitoring. The
(3) heterogeneous surface reaction catalyzed by the surface of the substrate, chemical reactions include pyrolysis,
(4) surface diffusion of the species to growth sites, oxidation, reduction, hydrolysis, or a
(5) nucleation and growth of the film on the substrate, and combination of these and may be
(6) desorption of gaseous reaction products and transport of reaction catalyzed by the substrate.
products away from the surface.
• Similar to PVD in that it is used to produce high-purity, specialized thin coatings, CVD
involves mixing the source material with one or more volatile precursors that functions as a
carrier device.
• These precursors, which are typically halides or hydrides, chemically interact and break
down the source material. The entire CVD process is known to generate volatile by-products
that must be safely removed via gas flow through the reaction chamber.
• Once created, the source material is transported into the reaction chamber, which contains a
substrate, by forced convection. Through the process of diffusion, reactants are deposited
into the substrate. After the mixture adheres to the substrate, the precursor eventually breaks
down, is removed by diffusion and leaves behind the desired layer of source material on the
substrate. The decomposition process can be facilitated or accelerated using heat, plasma
or various techniques.
• One of the biggest advantages of using CVD is that it can be used to evenly coat irregular
surfaces, including screw threads and recesses. The process is also extremely versatile; it
has been used with an extremely wide range of elements and compounds. CVD also
produces a thin film with very high purity and density. Because numerous parts can be
coated simultaneously, CVD is a relatively economical deposition process.
• CVD has been used across a wide range of industries. Some organizations use it to apply
coatings for wear resistance and temperature protection. Others use it to produce
semiconductors for electronic devices. CVD has also been used to fabricate dense structural
parts that are difficult or cost-prohibitive to make with conventional techniques.
Liquid Phase deposition
Liquid Phase deposition
Liquid Phase deposition
Liquid Phase deposition
 Langmuir – Blodgett films

Introduction
• Langmuir – Blodgett films are monofilms or multifilms on solid substrate.
• Molecules form a monolayer at the interface air-liquid
• They are nanomaterials
• The films are layers at scale 0,1 – 0,001 nm ( ~ 1 nm)
 Langmuir-Blodgett film
• Langmuir-Blodgett films are formed by the deposition of a Langmuir film onto a solid substrate.
• Langmuir films are composed of an organized monolayer of amphiphilic molecules at a liquid/gas
interface.
• These molecules, by virtue of possessing a hydrophobic tail and a hydrophilic head, are spontaneously
oriented at a liquid/gas interface.
• For example, a sparingly water-soluble amphiphile spread onto an aqueous phase results in partial
solubilization of the head group, while the hydrophobic tail group extends partially into the gaseous
phase to minimize the free energy of the system.
(loves water)

(hates water)
 Monolayer

This tendency can be explained by surface-energy considerations. Since the tails are hydrophobic, their exposure to air
is favoured over that to water. Similarly, since the heads are hydrophilic, the head–water interaction is more
favourable than head-air interaction. The overall effect is reduction in the surface energy (or equivalently, surface
tension of water).
Langmuir-Blodgett (LB) Films and Langmuir-Schaefer(LS)Films
Difference between Langmuir-Blodgett thin film technique , Spin and Dip Technique

Spin/Dip Coating Langmuir-Blodgett

Amount of material required High Low
Controlled packing density low high
Monolayer inspection prior
No Yes
deposition
Controlled multi-layer
Very low High
structures
Applications
 Applications

Energy
 Film Patterning
The primary goal in film growth is to cover the substrate surface with a highly uniform and
pure layer (or layers) of the desired composition and morphology, using minimal energy and
materials.
 Film Patterning

However, almost every conceivable electronic device requires patterning to define its
active area.

This requires the “definition of electrode size and shape, and often the active organic
material itself must be patterned to provide a well-defined path for optical, current or
thermal transfer”

Pattern sizes ranging from tens of nanometers to centimeters are common for
optoelectronic components, ranging from quantum-effect devices to large area lighting
appliances and solar cells.
 Film Patterning
An illustration of the challenges faced in patterning of electronic
devices is in defining the red (R), green (G), and blue (B) pixels
that comprise a full color OLED display.

These sub-pixel elements can be as small as 10 μm, depending

on the resolution and overall size of the display (larger displays
have larger pixels since the viewer is positioned farther from the
screen).

An example of the sub-pixel arrangement of an OLED display, and

a cross section illustrating the patterning challenges is shown in
Fig. 5.58.

A display requires patterning of millions of very small pixels precisely spaced across very large (several meters) substrates
at 100% yield. Pixel yield is the ratio of functioning devices to the total number fabricated.

Furthermore, materials used for one device (or pixel) must not cross over into the region of its neighbor. This cross-
contamination inevitably decreases the color purity of the image.

Hence, the multiscale fabrication challenges for patterning very small devices over very large substrates are peculiar to
the field of organic electronics, which uniquely benefits from scaling spatial dimensions over many orders of magnitude.
Film Patterning-Inkjet Printing
 Inkjet printing

Inkjet printing has gained a significant interest in recent years

for processing solution-based nanomaterials and patterning on
diverse substrates in a single step.

Nanoparticles of the functional materials are mixed in

compatible solvents to prepare printable ink. Besides, chemical-
based solutions are also prepared and adjusted to the jetting
parameters of the inkjet printing systems.

Schematic in Figure shows mechanism of droplet ejection

through piezoelectric/thermal inkjet material printer. Typical
nozzle diameters used for inkjet heads range from 10 to
150 μm and reservoir ink with a volume capacity of 3 ml.
 Inkjet printing

Mainly two mechanisms for the actuation of inkjet nozzle head

have been developed, i.e., thermal and piezoelectric.

The actuating element is either thermal or piezoelectric, in

case of thermal actuator, a filament is embedded in the nozzle
head, and upon the voltage application, a bubble is generated
in the nozzle that pushes ink to the nozzle tip and generates
droplets.

In case of piezoelectric element, piezoelectric crystal is

placed inside the nozzle, and upon the voltage application,
piezoelectric crystal vibrates, and as a result, pressure exerts
on the ink inside the nozzle and droplet generates.
 Inkjet printing Advantages

This technology is considered suitable for printed electronics due to the following
reasons:

•It is a non-contact process that selectively deposits a wide range of materials

onto a wide range of substrates in a drop-by-drop manner.

•The shop floor space requirements, the initial investment as well as the
commissioning time to get an inkjet printing setup running are lower than most
other printing technologies.

•It is suitable for a wide range of production scales, from prototyping to large-
scale industrial production.

•Ink consumption and material wastage are minimal.

•It is flexible with regard to its positioning within a process chain.

 Inkjet printing Advantages

•It can produce patterned thin films - a key requirement for organic electronics. It should be
mentioned however, that manufacturing of highly complex integrated circuits (ICs) has
exclusively been performed by specialized techniques deviating from standard inkjet to meet
the requirements for a high spatial resolution for ultra-short transistor channel lengths.

Finally, it is possible to add functionalities using inkjet printing on a substrate that already has
electronic structures and devices, fabricated using any other technology.

Its non-contact, mask-less and master-less nature, along with the freedom to position the
printhead directly on top of any 3D coordinate of the substrate, enable this aspect.
Classification of the most common inkjet printing
technologies.
 Continuous Ink Jet Printing

In spite of the very high droplet generation frequencies (20-60 kHz), CIJ printing is not widely
used in printed electronics as the recycling process after exposure to the environment might
result in contamination of the ink. Moreover, CIJ is a potentially wasteful process, as a result
of continuous generation of droplets irrespective of presence or absence of information at
each pixel of the image or the text to be reproduced. However, CIJ has its advantage when it
comes to work on substrates with a non-planar geometry.
 Drop on Demand Ink Jet Printing
As far as the DOD inkjet technologies are concerned,
thermal inkjet and electrostatic inkjet lag far behind
the piezo inkjet, mainly due to the following reasons:

• Thermal inkjet can lead to degradation of

functional materials present in the ink due to the
cyclic thermal loading. Piezo inkjet, on the other
hand, is an isothermal process.
• Nontheless, thermal inkjet has successfully
proven suitable for the manufacturing of light-
emitting diodes based on inorganic quantum dots.
• The range of ink solvents that could be used in
piezo inkjet is much broader than thermal and
electrostatic inkjet.
• The investment and running costs needed for an
electrostatic inkjet is much higher than piezo
inkjet. Moreover, this technique is still under
development, and is not as mature as either piezo
or thermal inkjet in its evolution.
Application Examples
There are numerous application examples that demonstrate the suitability of inkjet printing for
printed electronics; only a selected few are presented here.
Inkjet printing has been successfully used to fabricate passive electrical components. It has also
surpassed spin coating as an effective manufacturing method to fabricate organic or polymer light
emitting devices (OLED/PLED). In fact, high-resolution patterning of an allpolymer thin-film transistor
(TFT) using inkjet printing has already been achieved. However, these devices are currently
restricted to low-end applications e.g., radio frequency identification tags (RFID), as the active
materials they are made of have low mobility. Moreover, their switching speeds are low. Another
active area of research is solar energy. Inkjet-printed organic solar cells were demonstrated by
Konarka Technologies Inc. Research activities are currently underway to inkjet print high-efficiency
solar cells using inorganic materials.
 Shadow mask patterning
The most common means for patterning organic devices grown from the
vapor phase, and for depositing contacts to solution processed thin films,
is via the use of shadow masks.

The mask is comprised of a thin metal such as Mo.

The mask apertures through which material is deposited are defined by
conventional photolithography (lithography is explained latter).

The mask is placed in close proximity, or in contact with the substrate in

the direction facing the evaporation sources. In vacuum themal
evaporation (VTE), the evaporant travels ballistically along a line of sight
from source to substrate, depositing through the mask apertures.

VTE is done in a high vacuum environment, typically ranging from 10-6

torr, to ultrahigh vacuum (UHV) approaching 10-11 torr. When deposition
occurs at UHVs (loosely defined as pressures, P < 10-8 torr), the process is
known as organic molecular beam deposition (OMBD)
 Pattern Resolution

The pattern resolution is determined by the thickness of the mask, t, the

width of the aperture, w, the distance from source to substrate, h, the
separation between the mask and the substrate, s, and the linear dimension
of the source, l (see Fig. 5.59a).

Directly behind the aperture, the deposit reaches its full thickness that is
monitored in real time with a quartz crystal microbalance.

Due to the finite dimensions of s, t and l, some material is deposited in the

shadowed area, forming a penumbra of deposit of width (Shtein et al., 2003)

As the pattern size decreases, spreading of the deposit beneath the mask becomes a larger
fraction of w, ultimately limiting the achievable pattern resolution. To improve resolution (i.e.
by minimizing r), the mask thickness, t, and s also must be decreased, while l is increased,
although this latter dimension is fixed by the size of the vacuum system.
Photolithography
 Photolithography

• The word lithography comes from the Greek lithos, meaning stones, and graphia, meaning to
write. It means quite literally writing on stones. In the case of semiconductor lithography (also
called photolithography) our stones are silicon wafers and our patterns are written with a light
sensitive polymer called a photoresist.

• To build the complex structures/patterns that make up a transistor and the many wires that
connect the millions of transistors of a circuit, lithography and etch pattern transfer steps are
repeated at least 10 times, but more typically are done 20 to 30 times to make one circuit.

• Each pattern being printed on the wafer is aligned to the previously formed patterns and
slowly the conductors, insulators, and selectively doped regions are built up to form the final
device.
 Photolithography

The fabrication of an integrated circuit (IC) requires a variety of physical and chemical processes
performed on a semiconductor (e.g., silicon) substrate. In general, the various processes used to
make an IC fall into three categories: film deposition, patterning, and semiconductor doping.
Films of both conductors (such as polysilicon, aluminum, and more recently copper) and
insulators (various forms of silicon dioxide, silicon nitride, and others) are used to connect and
isolate transistors and their components. Selective doping of various regions of silicon allow the
conductivity of the silicon to be changed with the application of voltage.

By creating structures of these various components millions of transistors can be built and wired
together to form the complex circuitry of a modern microelectronic device. Fundamental to all of
these processes is lithography, i.e., the formation of three-dimensional relief images on the
substrate for subsequent transfer of the pattern to the substrate.
 Photolithography
• In integrated circuit manufacturing, photolithography or optical lithography is a general term used
for techniques that use light to produce minutely patterned thin films of suitable materials over a
substrate, such as a silicon wafer, to protect selected areas of it during subsequent etching,
deposition, or implantation operations.
• Typically, ultraviolet light is used to transfer a geometric design from an optical mask to a light-
sensitive chemical (photoresist) coated on the substrate.
• The photoresist either breaks down or hardens where it is exposed to light. The patterned film is
then created by removing the softer parts of the coating with appropriate solvents.

Conventional Photoresists typically consists of 3 components:

• Resin (a binder that provides mechanical properties such as adhesion, chemical resistance, etc),
• Sensitizer (which has a photoactive compound), and
• Solvent (which keeps the resist liquid)
Photolithographic
Patterning
 Positive Photoresist
When positive photoresist (Fig. 5.61a) is used;
The UV light breaks the photosensitive bonds in the polymer, making it vulnerable to solvent attack.
The sample is dipped into a solvent developer that dissolves the exposed areas, leaving the
unexposed regions untouched (“what shows, goes”).

The remaining photoresist pattern is the baked (i.e. cured) to render it chemically inert to process
chemicals that are used on the underlying substrate to replicate the pattern in the exposed areas.

Thus, pattern replication proceeds by dipping the sample into an acid, or exposing it to a reactive
gas that selectively attacks the semiconductor, but not the resist.

By this means, the open areas of the resist establish the same pattern in the semiconductor, with
pattern resolutions down to 10 nm. The final step is the removal of the photoresist by a second
chemical exposure, this time using one that does not damage the underlying semiconductor
 Negative Photoresist and Lift Off
Negative photoresists simply reverse the process, that is, the UV exposed areas cross-link the photopolymer
whose patterns then remain when developed (Fig. 5.61b).

Lift-off is the third process whereby a hard layer (e.g. a metal or a dielectric) coats the semiconductor along
with the pre-patterned resist surface (Fig. 5.61c). The resist is dissolved away beneath the coating, leaving it in
exposed areas of the semiconductor where the resist was previously removed. Lift-off provides high resolution
patterning of metals and insulators that are coated across the entire substrate surface
 A positive photoresist
A positive photoresist is a type of photoresist in which the portion of the photoresist that is exposed to
light becomes soluble to the photoresist developer. The unexposed portion of the photoresist remains
insoluble to the photoresist developer.
Photodecomposing photoresist is a type of photoresist that generates hydrophilic products under light.
Photodecomposing photoresists are usually used for positive photoresist.

A typical example is azide quinone, e.g. diazonaphthaquinone (DQ).

A negative photoresist
A negative photoresist is a type of photoresist in which the portion of the photoresist that is exposed to
light becomes insoluble to the photoresist developer. The unexposed portion of the photoresist is
dissolved by the photoresist developer.

Negative photoresist whereby the parts exposed to UV become cross-linked, while the remainder of the
film remains soluble and can be washed away during development.

Photocrosslinking photoresist is a type of photoresist, which could crosslink chain by chain when
exposed to light, to generate an insoluble network. Photocrosslinking photoresist are usually used for
negative photoresist.
E.g. : SU-8 is a commonly used epoxy-based negative photoresist.
Differences between positive and negative resist
Photolithography-Patterning of Organic Semiconductors
A major advantage enjoyed by photolithography is its very high resolution, and the ability to
sequentially add or remove layers in a multi-step patterning campaign, with each layer aligned to the
previous pattern to within only a few tens of nanometers. Hence, extraordinarily complex electronic
circuits have benefitted from the flexibility and versatility of this highly evolved patterning technology.

Unfortunately, photoresists are seldom employed in the patterning of organic semiconductors (except
in preparation of the substrate surface prior to organic film deposition) due to the likelihood of damage
from the wet chemistry involved in resist deposition, development and removal.

Organic semiconductors are often attacked by the same solvents as those used in photolithography.
This has led to modifications of conventional photolithography to achieve similarly high resolution
patterning of organics.
One method of achieving nanometer-scale features in small molecular weight semiconductors is to prepattern the
substrate surface itself using conventional photolithography prior to deposition of the active organic layers.
By deposition of the organic on the resulting substrate ridges or troughs, the film replicates the morphology of the
underlying topography, as shown in Fig. 5.62a.

A problem occurs when the organic is incident from a non-normal direction, as illustrated in Fig. 5.63a. This results in
shadowing from one of the sidewalls of the feature, breaking the deposit on only one feature edge, but giving
continuous coverage on the opposite sidewall. While this may not be a problem for resistive organics where lateral
conductivity along a sidewall is low, patterning a metal contact by this method to define the device area results in
shorts between adjacent devices.
 Photoresist Chemistry
Photoresists consist of polymer molecules dissolved in a
solvent. Three very simple polymer molecules are shown
here. H H
H H H H

C C C C C C
O
H H H H H H
H H H C OH

C C C C C C

H H H

The C’s represent carbon atoms, the H’s are hydrogen atoms, and the
hexagon is a 6-carbon ring. The pattern can repeat many thousands of times
in a polymer.
 Photoresist Chemistry
When light strikes these polymer molecules, they undergo a
chemical reaction. The type of reaction depends on the type of
resist used.
In a negative resist, light exposure may make the polymers crosslink, which
means they bond to neighboring molecules to form a strong network, like this:
H H H H H H

C C C C C C
C H H H H
C H
H C H
H C
H C
H C
H
H
These larger polymer molecules are much less soluble in a solvent (like the
developer). So any spot on the resist-coated wafer that was exposed to light will
not dissolve when the wafer is immersed in the developer solution. The
unexposed (and thus un-reacted) molecules, on the other hand, will dissolve away
in the developer.
 Photoresist Chemistry
When a positive resist is exposed to light, the polymer
molecules tend to break into smaller fragments.
H H H H H H

C C C C C C C C C C C C

H H H H H H

These smaller, lighter molecules are more likely to dissolve (or will
dissolve more quickly) in the developer. The reaction with light may also
create polar regions on the molecule, making it more likely to dissolve in
water or water –based solutions.

So any spot on the resist-coated wafer that was exposed to light will
readily dissolve when the wafer is immersed in the developer solution.
The unexposed resist molecules will remain on the wafer.
 Developer Chemistry
After the photoresist-coated wafer has been exposed to light, it
is immersed in a water-based solution called developer.
Photoresists are formulated so that the areas to be removed are
acidic. If these acidic areas are exposed to a basic (or alkaline)
solution, they will react and dissolve in the developer.

Molecule soluble
Acidic Base
O O in water
group
C OH C O- K+

KOH H2O

Developers are often basic solutions, such as potassium

hydroxide (KOH) or sodium hydroxide (NaOH) in water.
 Soft lithography
“Soft” means no energetic Soft lithography opportunity assessment
particles (electron, ions) or
radiation (UVs, X-ray) is
involved. Instead, soft
elastomeric stamp is used.

Soft lithography:
• Low cost
• Molding, printing or transferring
• Resolution usually not very high
• Application in microfluidic, biomedical …

George M. Whitesides (Harvard)

“Size is not the only thing that matters, function is more important” (something like this), Whiteside 62
 PDMS: poly(dimethyl-siloxane)
PDMS properties:
• Silicone elastomer with a range of viscosities
• Flexible (1 MPa Young’s modulus, typical polymer 1 GPa) and easy to mold.
• Elastomer, conforms to surface over large areas.
• Chemically inert, optically transparent
• Low surface energy: bonds reversibly (or permanent).
• Seals to flat and clean surfaces for micro-fluidic channels
• Durable (reusable), low thermal expansion
• Biocompatible (even used for food additive)
• Environmentally safe
• Best Resolution: 2-10 nm (for hard PDMS)

Dow Corning brand

63
 PDMS surface treatment

Upon treatment in oxygen plasma, PDMS seals

to itself, glass, silicon, silicon nitride, and some
plastic materials.

Plasma oxidation

Air (10 min)

contact PDMS surfaces

Irreversible seal:
formation of covalent bonds

Biggest issue: it becomes hydrophobic quickly, very bad for micro-fluidic applications.
(liquid hard to get into the channels once it becomes hydrophobic)
PMDS is absolutely the most popular material for bio-medical lab-on-chip (microfluidic) applications,
but may not be suitable for commercial applications, which need chemically stable surface.
64
 PDMS surface treatment
• PDMS has a low interfacial free energy such that molecules of most
polymers won’t stick on or react with its surface.
• The interfacial free energy can be manipulated with plasma treatment.
• For nano-imprint or soft lithography mold, plasma can make PMDS surface
like SiO2, easy for mold release agent coating using silane chemistry.

Silanization-
Adding a self-
assembled
monolayer (SAM) of
organosilanes to the
surface

Low surface energy if X=fluorocarbon

65
 PDMS fabrication

Cure on hotplate for few hours

Peel off PDMS

Master pattern (red color) can be in:

photoresist (SU-8), silicon, glass…
Besides casting, PDMS can also be spin- Silanization of master mold needed to obtain
coated to form thin (many m) films low surface energy for easy separation. 66
Figure 1 - "Inking" a stamp. PDMS Figure 2 - ODT from the solution settles down
stamp with pattern is placed in Ethanol onto the PDMS stamp. Stamp now has ODT
and ODT (octadecanethiol) solution attached to it which acts as the ink.

Figure 3 - The PDMS stamp with the

ODT is placed on the gold substrate.
When the stamp is removed, the ODT
in contact with the gold stays stuck to
the gold. Thus the pattern from the
stamp is transferred to the gold via the
ODT "ink."
Micro - contact printing (μCP)

20m 100mm stamp

68
 Micro - contact printing (μCP)

Test structures in Au, smallest dimension 400nm

69
Micro - contact printing (μCP), with roller

a. Printing on a planar surface with a

planar stamp.
b. Printing on a planar surface with a
rolling stamp
c. Printing on a non-planar surface
with a planar stamp

Xia & Whitesides, Angew. Chem. Int. Ed. 1998, 37, 550-575. 70
A. Kumar & G. Whitesides, Applied Physics Lett. 1993
 Micro - transfer molding (μTM)

Pre-polymer

PDMS

Substrate

• Apply the liquid prepolymer

• Planarize the prepolymer
• Place the master on a planar substrate
• UV exposure or heating solidifies the
prepolymer that sticks to the substrate

TM fabrication of a). one-layer microstructures;

b). three-layer polymer microstructures. 71
 Micro - transfer molding (μTM)

Microstructures fabricated using TM.

a) An SEM image of a fractured sample showing a
pattern of isolated stars of UV-cured polyurethane
(NOA 73) on Ag.
b) An array of parallel lines of spin-on glass on Si with an
aspect ratio (height/width) of 8.
c) A two-layer structure: isolated micro-cylinders (1.5m
in diameter) on 5m-wide lines, supported on a glass
cover slide.
d) A two-layer structure: a continuous web over a layer
of 5m-wide lines, supported on a glass cover slide.
e) A three-layer structure on a glass cover slide. The
layers of 4 m-wide lines are oriented at 60o from
each other.
Structures in c-e were made of heat-cured epoxy
(F109CLR).

72
Zhao & Whitesides et al, Advanced Materials, 1996, 8, 837.
Metal transfer assisted nanolithography

Glass transition temperature is 105oC

a) SEM image of the transferred metal grating onto

PMMA layer with period of 700nm on SiO2 substrate.
b) Period 220nm on PET substrate.
c) After O2 RIE of b.
d) After metallization and lift-off process of c.

73
Guo, “Metal transfer assisted nanolithography on rigid and flexible substrates”, JVST B, 2008
 Solvent assisted microcontact molding (SAMIM)
(solvent assisted imprinting)

Substrates
Silicon
Glass
Flexible transparency
Polymer
SU-8 (1μm)
Shipley 1805 Photoresist (500nm)
The molded polymer structure becomes solidified in a
3% PMMA (70nm)
few minutes after evaporation of solvent, while the
stamp is still in conformable contact with the substrate. Solvent
SU-8 (ethanol)
Shipley 1805 photoresist (ethanol)
3% PMMA (acetone)

Uses a solvent to wet the PDMS stamp and soften the structure polymer.
Dissipate and evaporate the solvent through PDMS.
(PDMS stamp can absorb the solvent because of the solvent permeability of PDMS.)
74
Kim & Whitesides et al, Advanced Materials, 1997, 9,651.
SAMIM of SU-8 in ethanol

2m diameter

SU-8

75
 SAMIM of PMMA in acetone

Au structure fabrication

76
 SAMIM of PMMA in acetone

Hole array in PMMA Au dot array after liftoff

Dot diameter 160nm.

77
 Soft lithography: advantages and disadvantages

Advantages:
Disadvantages:
• Convenient and low cost
• Distortion of patterns
• Rapid prototyping
• Poor registration/alignment
• Deformation of PDMS provides route to
• Poor compatibility with IC processes
complex patterns
• More defects and their densities
• Non-planar or curved surfaces
• μCP can only be applied to a limited
• Generation of 3D -structures
number of surfaces
• Control over surface chemistry
• It a is a relatively slow process
• A broad range of materials
• Applicable to manufacturing
• Patterning over large areas

78
 Self-Assembled Monolayers

Self-assembled monolayers (SAMs) are molecular layers that assemble on a surface by

adsorption, usually from solution. Their formation is mediated by a specific functional group that
has a strong affinity for a particular surface.

Most extensively investigated have been SAMs utilizing alkanethiolates and gold. When a
gold surface is immersed in a solution of alkane thiolates, the sulfur atoms coordinate to
the gold (111) surface in a densely packed array
Self-assembled monolayers (SAMs) are an important element of modern nanotechnology. Among other
applications, they can be used for the fabrication of monomolecular insulator films of well-defined
thickness in the sub-nm to few nm range to provide an alternative to commonly used oxide dielectrics in
future, nano-scale electronic and spintronic devices, and also in organic electronics assembles.

Additionally, SAMs can act as the active elements of such devices, in the framework of both molecular
electronics (molecules as individual devices) and organic electronics (SAM as an ultrathin organic
semiconductor).
Fig. 2 Top: On the left, sketch of a typical aliphatic self-assembling molecule: the three major components (head,
backbone and tail) are highlighted; on the right, some of the most common terminal groups and backbone for self-
assembly. Bottom: Some of the extensively used substrates for functionalization via self-assembly.
 SAMs in OLEDs and OPVs

Charge injection and transport are central issues also in

organic light emitting diodes (OLEDs) and organic photo-
voltaics (OPVs). In these devices, other phenomena enter
into play, like charge transfer between layers and
recombination of excitons. These phenomena also require
the control of energy levels at the interfaces and of the
characteristic length scales in p-conjugated thin films. The
enhancement of external quantum efficiency of OLEDs, due
to the control of the anode work function by means of azo-
benzene SAMs.

FIG. 1. (a) Current density-voltage plots and (inset) chemical structure of the
molecules used for the self-assembled monolayer, thiol-functionalized azo-
biphenyl (AZO-SAM 1, top), and fluorinated azo-benzene (AZO-SAM 2,
bottom); (b) (semi-logarithmic) luminance-voltage plots and (inset) scheme
of devices structure. Symbol code is the same in both panels.
SAM-modified organic field effect transistors

OSC = the organic semiconductor

 SAM as a functional coating of gate dielectrics

The interface between the gate dielectric and the OSC thin film is important for charge carrier transport in OFETs

The use of SAMs grafted onto the gate dielectrics is thus an effective route to passivate the dielectric surface from
undesired reactions and define its surface energy, thus getting rid of several of these problems at once.
Self assemble monolayer above the gate insulator
Self assemble monolayer- Managing hysteresis behavior
Hysteresis is the dependence of the state of a system on its history. Hysteresis can be a dynamic lag between an input
and an output that disappears if the input is varied more slowly; this is known as rate-dependent hysteresis.

Hysteresis is a common feature of many OTFTs, and results from trapping and detrapping of charge from the
semiconductor/insulator interface, or from within the semiconductor bulk.

Hysteresis is in general an unwanted effect, which makes the transistor parameters dependent on the gate voltage
sweep range, direction and time, and on the loading history.

Therefore, it should be minimized or eliminated to improve the device stability and reliability.

Forward I-V curve is

not equivalent to
reverse I-V curve.
Self assembled monolayer above the gate insulator-example

Hysteresis can be eliminated by reducing the trap/surface

defect density, as has been demonstrated through
incorporation of a high-quality hydrophobic organic layer
between nanotube and the SiO2. For this purpose, the Si/SiO2
(SiO2 = 4 nm) substrates have been covered by a selfassembled
monolayer (SAM) prepared from 18-
phenoxyoctadecyltrichlorosilane [43], as shown in Figure.

Semiconducting single-walled carbon nanotubes (s-SWCNTs)

 Cyclic Voltammetry (CV)
• CV is a technique works by varying the applied potential of the working electrode at a particular scan
rate (ν) in both forward and reverse directions while monitoring the current. The resultant trace of
current against potential is termed as a voltammogram.
• During cyclic voltammetry measurement, the potential is ramped from an initial potential, Ei, to a more
negative or positive potential but, at the end of the linear sweep, the direction of the potential scan is
reversed, usually stopping at the initial potential, Ei (or it may commence an additional cycle).
• The potential is applied between the reference electrode (RE) and the working electrode (WE), and the
resultant current between the working electrode and the counter electrode (CE) (auxiliary electrode) is
measured. This data is then plotted as current vs. potential.
• The forward scan produces a current peak for any chemical species that can be either reduction current
or oxidation current depending on the initial scan direction over the range of potential scanned. The
current increases as the potential reaches the reduction potential of the analyte, but then decreases as
the concentration of the analyte is depleted close to the electrode surface.
• If the redox couple is reversible, then reversing the applied potential makes it to reach a potential that
re-oxidizes the product formed in the first reduction reaction, thus producing a current of reverse
polarity from the forward scan. The oxidation peak usually has the same shape as that of the reduction
peak.
Profile of applied potential in CV and a typical cyclic voltammograms
Electrochemical work station or potentiostat
RSC Adv., 2022, 12, 1897–1903
Fig. 2. Electropolymerization on the PEDOT:PSS
layers. (a) Voltammogram of the electrochemical
oxidative polymerization of aniline from 2 to 10 cycles,
(b) optical images of the PEDOT:PSS-DMSO layers
with different polymerized cycles (3, 6, 10), SEM
images at different scales without electrodeposited
polyaniline in (c) and with polyaniline in (d). The
samples in (d) were obtained by 6-cycles
NiCo2O4 thin film prepared by electrochemical deposition as a hole-transport layer for efficient inverted
perovskite solar cells
Spinel NiCo2O4 is a promising p-type semiconductor for optoelectronic devices; however, it is difficult to
prepare uniform and large-area NiCo2O4 films, which hinders its application as a hole transport material for
perovskite solar cells . A low-cost electrochemical deposition (ECD) approach was developed to directly
prepare a uniform NiCo2O4 film on a fluorinedoped tin oxide (FTO) substrate

RSC Adv., 2022, 12, 12544–12551

 Examples of full device fabrication
The fabrication process involved in micro-organic field effect transistor (micro-)OFET is shown in Figure 14.2 and
based on the common approach: gate insulator (with gate electrode underneath) as substrate, then deposition
of organic material, then application of source and drain contacts, and finally connection of the OFET to three
leads.

DIP

Diindenoperylene (DIP)

(a) Thinning of the sapphire substrate from the backside to achieve a thin gate dielectric; (b)
mounting of the metal gate electrode by thermal evaporation; (c) deposition of the active DIP
layer by OMBD; (d) application of the source and drain top contacts by Au deposition using a
lithographic mask; e) electrical characterization.