Lecture-11

Superlattices, Self Assembly &

LB Films

Two-Dimensional Nanostructures Cont…

(Ref: Guozhong Cao;
Nanostructures & Nanomaterial: Synthesis, Properties & Applications)
 Super Lattices
• Structures composed of periodically alternating single crystal film layers.

• When both layers are relatively thick, properties of bulk materials are

observed due to the frequently synergistic extensions of the laws of property

mixtures that are operative.

• However, when the layers are very thin, quantum effects emerge, since the

wavefunctions of charge carriers in adjacent thin layers penetrate the barriers

and couple with one another.

• Such structures are mostly fabricated by MBE; however, CVD methods are

also capable of making superlattices.

• ALD is another unique technique in the fabrication of superlattice structures.

• Semiconductor superlattices can be categorized into compositional superlattices

and modulation doping, i.e. selective periodic doping, superlattice.

• The fabrication of semiconductor superlattices is basically the controlled

synthesis of band gap structures, which is also known as band gap engineering.

Superlattice crystal
Some examples of super lattice system structure of InGaO3(ZnO)5
 Self-Assembly
• Self-assembly is a generic term used to describe a process that ordered

arrangement of molecules and small components such as small particles

occurred spontaneously under the influence of certain forces such as

chemical reactions, electrostatic attraction and capillary forces.

• We will focus our discussion on the formation of monolayer or multiple

layers of molecules through self-assembly.

• In general, chemical bonds are formed between the assembled molecules &

the substrate surface, as well as between molecules in the adjacent layers.

• Therefore, the major driving force is the reduction of overall chemical potential.

• A variety of interactions or forces have been explored as driving forces for the

self-assembly of nanometer as the fundamental building blocks.

• The driving force for the self-assembly includes: electrostatic force,

hydrophobicity and hydrophilicity, capillary force and chemisorption.

• There are several types of self-assembly methods for the organic monolayers

and these include (i) organosilicon on hydroxylated surfaces, such as SiO2 on Si,

Al2O3 on Al, glass, etc. (ii) alkanethiols on gold, silver and copper. (iii) dialkyl

sulfides on gold. (iv) dialkyl disulfides on gold (v) alcohols and amines on

platinum, and (vi) carboxylic acids on aluminum oxide and silver.

• Another way to group the self-assembly methods could be based on the types

of chemical bonds formed between the head groups and substrates.

• Three different ways are mentioned below:

(i) Covalent Si-0 bond between organosilicon on hydroxylated substrates

that include metals and oxides,

(ii) Polar covalent S-Me bond between alkanethiols, sulfides and noble

metals such as gold, silver, platinum and copper, and

(iii) Ionic bond between carboxylic acids, amines, alcohols on metal or

ionic compound substrates.

 Langmuir-Blodgett Films
• Langmuir-Blodgett films (LB films) are monolayers and multilayers of

amphiphilic molecules transferred from the liquid-gas interface (commonly

water-air interface) onto a solid substrate and the process is generally

referred to as Langmuir-Blodgett technique (LB technique).

• Langmuir carried out the first systematic study on monolayers of

amphiphilic molecules at the water-air interface and the first study on a

deposition of multilayers of long-chain carboxylic acid onto a solid

substrate was carried out.

• The amphiphile is a molecule that is insoluble in water, with one end that is

hydrophilic, preferentially immersed in the water and the other that is

hydrophobic, preferentially resides in the air or in the nonpolar solvent.

• A classical example of an amphiphile is stearic acid, C17H35COOH.

• In this molecule, the long hydrocarbon tail, C17H35 - is hydrophobic, and the

carboxylic acid head group, -COOH is hydrophilic.

• Since the amphiphiles have one end that is hydrophilic and the other that is

hydrophobic, they like to locate in interfaces such as between air and water,

or between oil and water.

• This is the reason they are also called surfactants.

• The solubility of an amphiphilic molecule in water depends on the balance

between the alkyl chain length and the strength of its hydrophilic head.

• Certain strength of the hydrophilic head is required to form LB films.

• If the hydrophilicity is too weak, no LB film can be formed.

• However, if the strength of the hydrophilic head is too strong, the

amphiphilic molecule is too soluble in water to allow the formation of a

monolayer.

• Table summarizes the properties of different head groups.

• The soluble amphiphile molecules may form micelles in water when their

concentration exceeds their critical micellar concentration.

The effect of different functional groups on LB film formation of C16-compounds
• The LB technique is unique, since monolayers can be transferred to many

different substrates.

• Most LB depositions have involved hydrophilic substrates where the

monolayers are transferred in the retraction mode.

• Glass, quartz and other metal substrates with an oxidized surface are used

as substrate, but silicon wafer with a surface of silicon dioxide is the most

commonly used substrate.

• Gold is an oxide-free substrate and also commonly used to deposit LB films.

• However, gold has a high surface energy (~ 1000 mJ/m2) and is easily

contaminated, which results in an uneven quality of LB films.

• Cleanliness of the substrate surface is crucial to high quality LB films.

• In addition, the purity of the organic amphiphiles under study is of great

importance, since any contamination in the amphiphile will be incorporated

into the monolayer.

• Figure schematically shows the formation of Langmuir films, which denote the

molecular films at the water-air interface.

• A drop of a dilute solution of an amphiphilic molecule in a volatile solvent, such

as CHCl3, is spread on the water-air interface of a trough.

• As the solvent evaporates, amphiphilic molecules are dispersed on the interface.

• The barrier moves and compresses the molecules on the water-air interface; the

intermolecular distance decreases and the surface pressure increases.

Schematic showing the formation of Langmuir films, which denote the molecular
films at the water-air interface, a drop of a dilute solution of an amphiphilic molecule
in a volatile solvent, such as CHCl3, is spread on the water-air interface of a trough.
• A phase transition may occur, which is assigned to a transition from the

“gas” to the “liquid” state.

• In the liquid state, the monolayer is coherent, except the molecules occupy

a larger area than in the condensed phase.

• When the barrier compresses the film further, a second phase transition can

be observed from the “liquid” to the “solid” state.

• In this condensed phase, the molecules are closely packed and uniformly

oriented.
• Two methods are commonly used to transfer monolayers from the water-air

interface onto a solid substrate.

• The more conventional method is the vertical deposition as sketched below:

The more conventional vertical deposition method for the

formation of LB films on substrates.
• When a substrate is moved through the monolayer at the water-air interface, the

monolayer can be transferred during emersion (retraction or upstroke) or

immersion (dipping or down stroke).

• A monolayer usually will be transferred during retraction when the substrate

surface is hydrophilic, and the hydrophilic head groups interact with the surface.

• However, if the substrate surface is hydrophobic, the monolayer will be

transferred in the immersion, & hydrophobic alkyl chains interact with the surface.

• If the deposition process starts with a hydrophilic substrate, it becomes

hydrophobic after the first monolayer transfer, and thus the second monolayer will

be transferred in the immersion.

• Multiple layer films can be synthesized just by repeating the process.

• Another method to build LB multilayer

structure is the horizontal lifting, also

referred to as Schaefer’s method.

• Schaefer’s method is useful for the

deposition of very rigid films.

• In this method as shown in Fig., a

compressed monolayer is first formed at the

water and air interface.

• A flat substrate is placed horizontally on the

Schaefer’s method useful for the deposition
of very rigid films, in which, a compressed
monolayer film. monolayer is first formed at the water and air
interface, a flat substrate is placed
horizontally on the monolayer film.
• When the substrate is lifted and separated from the water surface, the

monolayer is transferred onto the substrate.

• Thermal stability and order-disorder transition are two important issues for

any practical applications of LB films.

• Although a lot of research has been done in the past two decades, many

issues remain unsolved and our understanding on the structures and

stability of LB films is still very limited.

Prof. S. K. Tripathi

Department of Physics
School of Physical Sciences
Mahatma Gandhi Central University

Course Name: Nano Materials and Applications

Course Code: PHYS3024