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Layer-by-layer (LbL) deposition is a
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 ap ...
fabrication technique. The films are formed by depositing alternating layers of oppositely charged materials with wash steps in between. This can be accomplished by using various techniques such as immersion, spin, spray, electromagnetism, or fluidics.


Development

The first implementation of this technique is attributed to J. J. Kirkland and R. K. Iler of
DuPont DuPont de Nemours, Inc., commonly shortened to DuPont, is an American multinational chemical company first formed in 1802 by French-American chemist and industrialist Éleuthère Irénée du Pont de Nemours. The company played a major role in ...
, who carried it out using microparticles in 1966. The method was later revitalized by the discovery of its applicability to a wide range of
polyelectrolyte Polyelectrolytes are polymers whose repeating units bear an electrolyte group. Ion#Anions and cations, Polycations and polyanions are polyelectrolytes. These groups dissociation (chemistry), dissociate in aqueous solutions (water), making the pol ...
s by
Gero Decher Gero Decher is a German chemist and Distinguished Professor ("Professeur classe exceptionnelle") at the Faculty of Chemistry of University of Strasbourg. He is best known for his seminal role in the development of polyelectrolyte multilayers, whi ...
at
Johannes Gutenberg-Universität Mainz The Johannes Gutenberg University Mainz (german: Johannes Gutenberg-Universität Mainz) is a public research university in Mainz, Rhineland Palatinate, Germany, named after the printer Johannes Gutenberg since 1946. With approximately 32,000 stud ...
.


Implementation

A simple representation can be made by defining two oppositely charged polyions as + and -, and defining the wash step as W. To make an LbL film with 5 bilayers one would deposit W+W-W+W-W+W-W+W-W+W-W, which would lead to a film with 5 bilayers, specifically + - + - + - + - + - . It is important to note that the representation of the LbL technique as a multilayer build-up based solely on electrostatic attraction is a simplification. Other interactions are involved in this process, including hydrophobic attraction. Multilayer build-up is enabled by multiple attractive forces acting cooperatively, typical for high-molecular weight building blocks, while electrostatic repulsion provides self-limitation of the absorption of individual layers. This range of interactions makes it possible to extend the LbL technique to hydrogen-bonded films, nanoparticles, similarly charged polymers, hydrophobic solvents, and other unusual systems. The bilayers and wash steps can be performed in many different ways including
dip coating image:Dip coating.svg, A schematic of the continuous dip coating process. Roll of coarse cloth Cloth Bath Liquid material Rollers Oven Scrapers Excess liquid falls back A coating remains on the fabric cloth. Dip coating is an industrial ...
,
spin-coating Spin coating is a procedure used to deposit uniform thin films onto flat substrates. Usually a small amount of coating material is applied on the center of the substrate, which is either spinning at low speed or not spinning at all. The substrate ...
, spray-coating, flow based techniques and electro-magnetic techniques. The preparation method distinctly impacts the properties of the resultant films, allowing various applications to be realized. For example, a whole car has been coated with spray assembly, optically transparent films have been prepared with spin assembly, etc. Characterization of LbL film deposition is typically done by optical techniques such as
dual polarisation interferometry Dual-polarization interferometry (DPI) is an analytical technique that probes molecular layers adsorbed to the surface of a waveguide using the evanescent wave of a laser beam. It is used to measure the conformational change in proteins, or othe ...
or
ellipsometry Ellipsometry is an optical technique for investigating the dielectric properties (complex refractive index or dielectric function) of thin films. Ellipsometry measures the change of Polarization (waves), polarization upon reflection or transmissi ...
or mechanical techniques such as
quartz crystal microbalance A quartz crystal microbalance (QCM) (also known as ''quartz microbalance'' (QMB), sometimes also as ''quartz crystal nanobalance'' (QCN)) measures a mass variation per unit area by measuring the change in frequency of a quartz crystal resonator. The ...
. LbL offers several advantages over other
thin film deposition 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 ap ...
methods. LbL is simple and can be inexpensive. There are a wide variety of materials that can be deposited by LbL including polyions, metals, ceramics, nanoparticles, and biological molecules. Another important quality of LbL is the high degree of control over thickness, which arises due to the variable growth profile of the films, which directly correlates to the materials used, the number of bilayers, and the assembly technique. By the fact that each bilayer can be as thin as 1 nm, this method offers easy control over the thickness with 1 nm resolution.


Applications

LbL has found applications in protein purification, corrosion control, (photo)electrocatalysis, biomedical applications, ultrastrong materials, and many more. LbL composites from graphene oxide harbingered the appearance of numerous graphene and graphene oxide composites later on. The first use of reduced graphene oxide composites for lithium batteries was also demonstrated with LbL multilayers.


See also

*
Atomic layer deposition Atomic layer deposition (ALD) is a thin-film deposition technique based on the sequential use of a gas-phase chemical process; it is a subclass of chemical vapour deposition. The majority of ALD reactions use two chemicals called precursors (also ...


References

{{Reflist Thin films