LITHOS-'stone'

GRAPHO-'to write

Method of PRINTING by using

LITHOGRAPHIC STONE(LIMESTONE) METAL PLATE

IMAGE (ON WAX OR OILY SUBSTANCE) Transfer

MEDIUM (LITHOGRAPHIC STONE OR METAL PLATE)

Printed

PRINTED SHEET

IMAGE (POLYMER)
HYDROPHILIC -ACCEPT WATER -REJECTS INK

MEDIUM (ALUMINIUM PLATE)

HYDROPHOBIC -ACCEPT INK -REJECTS WATER

PRINTED SHEET

FLEXIBLE SHEET (RUBBER)

PRINTED SHEET

It uses chemical processes to create an image.

Parts of an image: Positive part Negative image

- Hydrophobic water hating substance. - Hydrophilic "water loving substance.

When the plate is introduced to printing ink and water mixture, the ink will adhere to the positive image and the water will clean the negative image.
This allows a flat print plate to be used, enabling much longer and more detailed print runs.

It refers to PHOTOLITHOGRAPHY AND DIRECT BEAM LITHOGRAPHY

A microfabrication technique used to make

Integrated circuits MEMS (microelectromechanical systems).

Cleaning Preparation

BASIC PROCEDURE

Photoresist application

Exposure and developing

Etching

Photoresist removal

1.CLEANING
To remove Organic or Inorganic contaminations present on the wafer surface

Usually by Wet chemical treatment

2.PREPARATION
Heat treatment to remove moisture from wafer.
Adhesion promoters added to promote adhesion of photoresist on wafer.
EX: ADHESION PROMOTER hexamethyldisilazane (HMDS)

Silicon dioxide layer on the wafer reacts with the agent to form Methylated Siliconhydroxide, a highly water repellent layer, to protect from aqueous developers.

3.Photoresist application

The wafer is covered with photo resist by spin coating. STEPS

A viscous, liquid solution of photo resist is dispensed onto the wafer, and the wafer is spun rapidly to produce a uniformly thick layer. Speed - 1200 -4800 rpm Time - 30-60 seconds Layer Thickness - 0.5-2.5 micrometres Prebaked :The photo resist-coated wafer is then prebaked to drive off excess photoresist solvent Temp - 90 to 100 C Time - 30 to 60 seconds

4. Exposure and developing

Photoresist is exposed to a pattern of intense light (Through Mask). Photolithography typically uses ultraviolet light. A pattern from the mask is copied on the photoresist by the light. Photoresist is then developed in developer depending upon the type of photoresist used. Exposer of light makes bonds of positive photoresist weaker and that of the negative photoresist stronger, where it falls on it.

 Mask
An opaque plate with holes or transparencies that allow light to shine through in a defined pattern. Consists of transparent fused silica blanks covered with a pattern defined with a chrome metal absorbing film.
MASK
(WITH PATTERN)

PHOTORESIST Photoresist
Positive photoresist Negative photoresist

(AFTER DEVELOPMENT)

- Soluble in the basic developer when exposed - Insoluble in the (organic) developer. - A solution used to remove unwanted photoresist.

Developer

5.Etching

A liquid ("wet") or plasma ("dry") chemical agent removes the uppermost layer of the substrate in the areas that are not protected by photoresist.

6. Photoresist removal

After a photoresist is no longer needed, it must be removed from the substrate. Liquid resist stripper : It chemically alters the resist so that it no longer adheres to the substrate.

Also known as Maskless lithography. The radiation is not transmitted through, a photomask, instead, the radiation is focused to a narrow beam. The beam is then used to directly write the image into the photoresist. Other procedure are same as in photolithography. Different types of direct beam lithography: Electron beam lithography Optical (direct laser) lithography Focused ion beam Probe tip contact

 Contains one or more monolayers of an organic material.

Deposited from the surface of a liquid onto a solid by immersing the solid substrate into the liquid.
A monolayer is adsorbed homogeneously with each immersion step, thus films with very accurate thickness can be formed. The thickness is accurate because the thickness of each monolayer is known. The monolayers are assembled vertically and are usually composed of AMPHIPHILIC MOLECULES.

PHYSICAL INSIGHT
LB films are formed when amphiphilic molecules (surfactants) interact with air at an air-water interface.

Surfactants are molecules

SURFACTANTS (SURFACE ACTING AGENT)
HYDROPHILIC HEAD HYDROPHOBIC TAIL

When surfactant concentration is less than critical micellar concentration (CMC), the surfactant molecules arrange themselves as shown in Figure
Hydrophobic tails favoured the tail-air interaction Hydrophilic head favoured the head-water interaction The overall effect is reduction in the surface energy (or surface tension of water).

LB films

Micelle
CMC: The concentration of surfactants above which micelles are spontaneously formed . Micelle: An aggregate of surfactant molecules dispersed in a liquid colloids

Langmuir-Blodgett trough

It is a laboratory apparatus Used to compress monolayers of molecules on the surface of a given subphase (usually water) and measures surface phenomena due to this compression. It can also be used to deposit single or multiple monolayers on a solid substrate.

1. Amphiphilc monolayer

2. Liquid subphase 3. LB Trough 4. Solid substrate 5. Dipping mechanism 6. Wilhelmy Plate 7. Electrobalance 8. Barrier 9. Barrier Mechanism 10. Vibration reduction system 11. Clean room enclosure

DEPOSITION

MONOLAYER
COMPRESSION

It is important to maintain constant surface pressure during deposition in order to obtain uniform LB films. Measurement of surface pressure can be done by means of a Wilhelmy plate (or Langmuir balance).

The surface tension calculated by the following equation:

Wilhelmy plate

l = (2w + 2d) w = width d = thickness

Defined as spontaneous and reversible organization of molecular units into ordered structures by non-covalent interactions (local interaction) without external direction

For self assembly subunits need certain properties like: Charge, polarizability, magnetic dipole, specific surface properties.
Self-assembly can be classified as: Static self-assembly system: It involves system that are at local equilibrium and do not dissipate energy. Formation of structure needs energy but once it is formed, it becomes stable. Dynamic self-assembly structures : The interactions responsible for the formation of patterns between components only occur if the system is dissipating energy. Example: Formation of Molecular crystals, colloids, lipid bilayers, and self-assembled monolayers.

There are at least three distinctive features of SA Order It must have a higher order than the isolated components.

Interactions Aspect of SA is the key role of weak interactions (e.g. Van der Waals, capillary, , hydrogen bonds) with respect to more "traditional" covalent, ionic or metallic bonds. Building blocks The building blocks are not only atoms and molecules, but span a wide range of nano and mesoscopic structures, with different chemical compositions, shapes and functionalities.

It has three main properties

Weak interactions: Self-assembling molecules adopt a structure, finding the best combination of interactions between subunits but not forming covalent bonds between them. Thermodynamic stability: For SA to take place without intervention of external forces, the process must lead to a lower Gibbs free energy, thus self-assembled structures are thermodynamically more stable than the single, unassembled components. Reversibility The weak nature of interactions is responsible for the flexibility of the architecture and allows for rearrangements of the structure in the direction determined by thermodynamics. If fluctuations bring the thermodynamic variables back to the starting condition, this leads to reversibility

SELF ORGANIZATION Non-equilibrium process

SELF ASSEMBLY Equilibrium process

Components changed

Components remain unchanged

No. of components very large

No. of components comparatively less

An organized layer of amphiphilic molecules, shows a special affinity for a substrate.

Formed by the chemisorption of hydrophilic head groups onto a substrate followed by a slow two-dimensional organization of hydrophobic tail groups.

The monolayer packs tightly due to van der walls interaction, thereby reducing its own free energy and are more stable than the physisorbed bonds of LangmuirBlodgett films.

A. Locally attract It involves locally depositing self-assembled monolayers on the surface only where the nanostructure will later be located.

The major techniques are: 1. Micro-contact printing Micro-contact printing is analogous to printing ink with a rubber stamp. The SAM molecules are inked onto an pre-shaped elastomeric stamp with a solvent and transferred to the substrate surface by stamping. The transfer of the SAMs is a complex diffusion process that depends on the type of molecule, concentration, duration of contact, and pressure applied. Typical stamps use PDMS (Polydimethylsiloxane)

Figure 1 "Inking" a stamp. PDMS stamp with pattern is placed in Ethanol and ODT (octadecanethiol) solution

Figure 2 ODT from the solution settles down onto the PDMS stamp. Stamp now has ODT 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

2. DIP PEN LITHOGRAPHY It uses an atomic force microscope to transfer molecules on the tip to a substrate. Tip (Dipped into a reservoir with an ink and molecules) EVAPORATION

Tip (only with the desired molecules )

Surface
Diffusion of molecules from tip to surface due resulting due to a water meniscus forms between the tip and the surface.
Meniscus :The curved upper surface of a non-turbulent liquid in a vertical tube

Tip radii: ~10 nm

B. Locally remove It begins with covering the entire surface with a SAM. Then individual SAM molecules are removed from locations where the deposition of nanostructures is not desired.

The major techniques that use this strategy are: 1. Scanning tunneling microscope (STM) a. Remove SAM molecules mechanically by dragging the tip across the substrate surface. b. Degrade the SAM molecules by shooting them with an electron beam.

STM

2. Atomic force microscope (AFM) Removal of SAM molecules by this method is called shaving. AFM tip is dragged along the surface mechanically removing the molecules. When the tip is brought into proximity of a sample surface, forces between the tip and the sample lead to a deflection of the cantilever according to Hooke's law.

F=Restoring force x=displacement k=force constant

It can also remove SAM molecules by local oxidation nanolithography.

3. Ultraviolet irradiation UV light is projected onto the surface with a SAM through a pattern of apperatures in a chromium film. This leads to photo oxidation of the SAM molecules. These can then be washed away in a polar solvent. Exposure time :15-20 minutes.

Control of wetting and adhesion Chemical resistance Bio compatibility Sensitization Molecular recognition for sensors and nano fabrication.