Layer-by-Layer Adsorption (LbL): An Enabling Technology ... · Institut Charles Sadron 5...

1Institut Charles Sadron

An Introduction to Polyelectrolyte An Introduction to Polyelectrolyte MultilayersMultilayers

Layer-by-Layer Adsorption (LbL):

An Enabling Technology for the Nano-construction of Multifunctional Filmson Solvent Accessible Surfaces.

G. Decher / Institut Charles Sadron


Some trivia:

• Surface functional groups accessible only from the solution side.( SN1 might be favored over SN2 ; reactivities different from bulk)

• Typical monolayer thicknesses of 0.5 nm to 5 nm.

• Typical surface areas of 0.20 nm2 per molecule, 5 1014 molecules per cm2.

• At a mass of 400 g/mol, 1 cm2 of a densely packed monolayercorresponds to 0.33 µg of material.

• 5g (semi-preparative scale), would cover an area of 1500 m2.

• Monomolecular layers of polymer may be thinner and less dense and typically consist of 0.1 to 1.5mg of material per 1 m2.

• Less than 0.02 mg for chemical analysis and physical characterization

Differences between chemistry in bulk and at interfaces

Advantage: We only need tiny amounts from colleagues doing synthesis


Build-to-Order Assembled Films

Build-to-Order (BTO) is the capability to quickly build standard or

mass-customized products upon receipt of spontaneous orders without

forecasts.

Layer-by-Layer assembly allows to design functional surfaces and

surface-based nano-devices in a "build-to-order" fashion. It exceeds

simple self-organization under equilibrium conditions by making it possible

to arrange many different materials at will with nanoscale precision.


Pierre Schaaf, Gero Decher, Jean-Claude Voegel

La Recherche, No. 389, SEPT. 2005, 56-58

The multilayer films that can do everything . . .


A Disruptive A Disruptive Nano-Coating Nano-Coating TechnologyTechnology

Layer-by-layer deposition can provide solutions in two areas:Layer-by-layer deposition can provide solutions in two areas:

•• Surface modificationSurface modification

(engineering the interaction of a given object with its environment) (engineering the interaction of a given object with its environment)

•• Fabrication of thin film devicesFabrication of thin film devices

(permitting (permitting multimaterial multimaterial assemblies including proteins and colloids)assemblies including proteins and colloids)

Applications:Applications: anticorrosion, antireflective coatings,anticorrosion, antireflective coatings,

biocompatibilisationbiocompatibilisation, biosensors, implants,, biosensors, implants,

optical waveguides, electroluminescent devices,optical waveguides, electroluminescent devices,

microreactorsmicroreactors, and many more , and many more ……

The ease by which even The ease by which even multimaterial multimaterial coatingscoatings can be put together using an can be put together using an

environmentally friendly low cost techniqueenvironmentally friendly low cost technique has kindled widespread interest, not has kindled widespread interest, not

only in academia. The first commercial products have already been introduced to theonly in academia. The first commercial products have already been introduced to the

market in 2001, 2002 and 2004.market in 2001, 2002 and 2004.


Schematic of the Layer-by-Layer Deposition ProcessSchematic of the Layer-by-Layer Deposition Process

Simplified Simplified ““molecularmolecular””

picture of the first twopicture of the first two

adsorption steps depictingadsorption steps depicting

film deposition as startingfilm deposition as starting

with a positively chargedwith a positively charged

substrate. substrate. Counterions Counterions areare

omitted for clarity.omitted for clarity.

Polyion Polyion conformation isconformation is

highly idealized and layerhighly idealized and layer

interpenetration is notinterpenetration is not

shown in order to bettershown in order to better

represent the surfacerepresent the surface

charge reversal with eachcharge reversal with each

adsorption step.adsorption step.

G. Decher, Science 277, 1232-1237 (1997)

> 1750 ISI-Citations (as of January 2006)


LbL LbL is (analogous to) a chemical reaction !is (analogous to) a chemical reaction !

Molecular scale Nano (meso) scale

Classic Synthesis

Reagent(s)(atoms, synthons)

series of

reactionsteps

Product(s)(typically single species)

LbL - Deposition

Surface(template)

Multilayer Film(defined layer sequence)

series ofdeposi-

tion steps

Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-VCH: Weinheim, 2003; 524 pages.


An Unprecedented Number of An Unprecedented Number of ““ReagentsReagents““ for for LbL-DepositionLbL-Deposition

Reagents: polymers

colloids

biomacromolecules

small molecules

small & complex ions

linearbranched(starshaped)copolymers

tacticitydegree of polymerizationcompositionmonomer sequence

polymericmetallicoxidic

proteinspolynucleotidesbioaggregates

sizepolydispersity

compositionsurface functionality

. . .

. . .

. . .



An Example of the integration of nanoparticles into the films

Schmitt, J.; Decher, G.; Dressik, W. J.; Brandow, S. L.; Geer, R. E.; Shashidhar, R.; Calvert, J. M.

Metal Nanoparticle/Polymer Superlattice Films: Fabrication and Control of Layer Structure. Adv. Mater. 1997, 9, 61-65.


LbL LbL Deposition (Programmed Assembly)Deposition (Programmed Assembly)

Advantages: deposition on surfaces of almost any kind and any shape

broad processing window

many control parameters: concentrationadsorption timeionic strengthsolvent compositiontemperature. . .



A bit of History (1):A bit of History (1):

It all started with It all started with ““BolaBola””-Amphiphiles-Amphiphiles

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0 5 10 15 20 25 30 35 40

Abs. biphenyl @ 262 nm

Ab

sorb

ance

@ 2

62 n

m

Su

bstrate

Adsorption

Bola-dication

Adsorption

Bola-dianion

G. Decher, J.-D. Hong, Makromol. Chem., Macromol. Symp. 46, 321-327 (1991)

420 ISI-Citations (as of January 2006)

Number of Layers



the next step were mixed bola/polyelectrolyte filmsthe next step were mixed bola/polyelectrolyte films

0.00

0.02

0.04

0.06

0.08

0.10

0 1 2 3 4 5 6 7 8

Abs. phenyl @ 225 nm

Abs. biphenyl @ 262 nm

Ab

sorb

ance

G. Decher, J.-D. Hong, Ber. Bunsenges. Phys. Chem. 95, 1430-1434 (1991)


Adsorption

Polyanion

Adsorption

Bola-dication

Number of Layers



and finally and finally polyanion/polycation multilayerspolyanion/polycation multilayers

0.00

0.05

0.10

0.15

0 5 10 15 20 25 30 35 40

Abs. phenyl @ 225 nm

Number of Layers

Ab

sorb

ance

@22

5 n

m

G. Decher, J.-D. Hong, J. Schmitt, Thin Solid Films 210/211, 831-835 (1992)


Adsorption

Polyanion

Adsorption

Polycation


A Small List of A Small List of Polyions Polyions Already Used for Multilayer FabricationAlready Used for Multilayer Fabrication

SO3- Na+

NN

OH

CO2-

NH

SO2

NH3+ Cl-

S+

N

OSO3- Na+

N

N

HO3S

SPAN

S+

N

PAMPSA

PEI

R

PMPyA R-PHPyV

H

N

PAZO

PAH

I -

Cl -

Pre-PPV

+

PSMDEMA

S

O- Na+

O NHO

HO3S

N

HN

N

HN

+

NH2

+ •

N

H2N

Cl -

Cl -

NH2

+

NH

HN

+

SO3-

PAPSA PTAANaPSS PVS

PDDA

Na+


Fine-tuning the film thickness by ionic strength (X-ray Fine-tuning the film thickness by ionic strength (X-ray reflectometryreflectometry))

(Addition of salt yields thicker layers; polyanion from salt, polycation from pure water)

10-3

10-1

101

103

105

107

109

1011

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

Ref

lect

ed X

-ray

Int

ensi

ty [

a.u.

]

16 alt. layers

Scattering Angle 2 [deg.]

12 alt. layers

20 alt. layers

30 alt. layers

42 alt. layers

50 alt. layers

100

200

300

400

500

600

5 10 15 20 25 30

1.0 m NaCl (17.7 Å / layer pair) 1.5 m NaCl (19.4 Å / layer pair) 2.0 m NaCl (22.6 Å / layer pair)

Film

Thi

ckne

ss [

Å]

Number of PSS-Layers

G. Decher and J. Schmitt, Progr. Colloid Polym. Sci. 89, 160-164 (1992)



Inversion of surface charge with deposition of each layerInversion of surface charge with deposition of each layer

-40

-20

0

20

40

0 5 10 15 20 25 30 35 40

Ze

ta P

ote

nti

al

[mV

]

Number of Measurement

bare SiO2 surface

PEI

PAHPAH PAH PAH PAH

PSSPSS PSS PSS

PSS

Adsorption of Adsorption of polycationspolycations

poly(ethylene poly(ethylene imineimine) (PEI) and) (PEI) and

poly(poly(allyl allyl amine) (PAH) renders theamine) (PAH) renders the

surface positively charged. Thesurface positively charged. The

deposition of poly(styrene deposition of poly(styrene sulfonatesulfonate))

(PSS) yields a negative surface charge.(PSS) yields a negative surface charge.

Similar measurements were alsoSimilar measurements were also

obtained from other groups.obtained from other groups.

For a theory of surface chargeFor a theory of surface charge

inversion see inversion see M. Castelnovo and J. F.

Joanny, Langmuir 16(19), 7524-7532

(2000) and for a mechanism ofand for a mechanism of

multilayer formation see multilayer formation see J. B.

Schlenoff and S. T. Dubas,

Macromolecules 34(3), 592-598

(2001).

G. Ladam, P. Schaad, J. C. Voegel, P. Schaaf, G. Decher, and F. Cuisinier, Langmuir 16(3), 1249-1255 (2000).


QCM-D (Q-Sense D300), Q-Sense AB, Gothenburg, Sweden, unpublished data


Automatic Layer Deposition Using a Automatic Layer Deposition Using a ““DippingDipping”” Robot Robot

Automated deposition device, R&K Ultrathin Organic Film Technology, Berlin, Germany


Deposition conditions are (in general) not really crucialDeposition conditions are (in general) not really crucial

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

140

160

180

200

220

240

260

280

300

0.4 0.6 0.8 1.0 1.2 1.4 1.6

PEI/(PSS/PAH)5

on quartz from x M NaClmanual dipping; dried after every layer

A @ 226 nm D [Å]

A @

226

nm D

[Å]

cNaCl

y = m1 + m2*m0

ErrorValue

0.0020.054m1

0.0030.061m2

NA6.8405e-06Chisq

NA0.99822R

y = m1 + m2*m0

ErrorValue

1567m1

15146m2

NA243.12Chisq

NA0.98912R

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

140

160

180

200

220

240

260

280

300

0.4 0.6 0.8 1.0 1.2 1.4 1.6

PEI/(PSS/PAH)5

on quartz from x M NaClautomated device; no intermediate drying

A @ 226 nm D [Å]

A @

226

nm D

[Å]

cNaCl

y = m1+m2*m0

ErrorValue

0.0060.059m1

0.0060.063m2

NA4.3167e-05Chisq

NA0.98951R

y = m1+m2*m0

ErrorValue

174m1

1150m2

NA1.151Chisq

NA0.99995R

However, dependence on ionic strength is stronger than in one of the previous cases since both polyions are deposited from saline solutions


From Neutron Reflectivity Curves:From Neutron Reflectivity Curves:

Number of Number of Deuterated Deuterated Layers, Layer Positions and Layer ProfilesLayers, Layer Positions and Layer Profiles

10-5

10-3

10-1

101

103

105

107

0 0.02 0.04 0.06 0.08 0.1

Re

fle

cte

d I

nte

ns

ity

(N

eu

tro

n)

Qz [Å-1 ]

0.0 100

1.0 10-6

2.0 10-6

3.0 10-6

4.0 10-6

5.0 10-6

6.0 10-6

7.0 10-6

8.0 10-6

0 500 1000 1500 2000 2500S

catt

eri

ng

Len

gth

Den

sit

y

n [

Å-2

]

Z [Å]

M. Lösche, J. Schmitt, G. Decher, W. G. Bouwman, and K. Kjær, Macromolecules 31, 8893-8906 (1998)



Large surfaces are coated by spraying

Albert Izquierdo and Claudine Porcell


High-Speed Layer-by-Layer Deposition

A. Izquierdo, S. S. Ono, J.-C. Voegel, P. Schaaf, and G. Decher, Langmuir 2005, 21, 7558-7567

15 min. / layer 6 sec. / layer

50 -150 times faster


A “real world” Biomedical Application:Contact Lenses Equipped with a Multilayer Coating

Photo courtesy of L. Winterton (CIBA-Vision), presented on occasion of the 223rd ACS National meeting April 7-11, 2002.

Partially based on US Patent US 520 8111, G. Decher & J.-D. Hong


• Silicones are hydrophobic

• Notoriously non-wetting

• Require Surface modification

– Retain the key physical properties of the bulkwhile modifying only the outermost surface toachieve wettability

Surface Wettability



Contact angle measurements on an uncoated (left)and LbL coated contact lens (right)

Photos courtesy of L. Winterton (CIBA-Vision), presented on occasion of the 223rd ACS National meeting April 7-11, 2002.


Focus® Excelens™, a contact lens by CIBA-Vison.

After 12 years of steadily growing research in academia, CIBA-Vision announced the

first commercially available product equipped with a multilayer coating.




Film Architectures Allowing to Control the Access of Cells toNeighboring Functional Layers: Tailored Bio-Interfaces

Monocytes accessing an embedded layer of Protein A, by developing extensions called pseudopods.

This behavior is controlled/suppressed by choosing the chemical composition of the individual layers

within the film architecture.

N. Jessel, F. Atalar, Ph. Lavalle, J. Mutterer, G. Decher, P. Schaaf, J.-C. Voegel and J. Ogier

Adv. Mater. 15(9) (2003), 692-695


A

B

TNF- secretion as a function of layer composition

Poly-L-Lysine

Poly-D-Lysine

N. Jessel, F. Atalar, Ph. Lavalle, J. Mutterer, G. Decher, P. Schaaf, J.-C. Voegel and J. Ogier

Adv. Mater. 15(9) (2003), 692-695


A A ““real worldreal world”” Application : Application :

““Yasa-SheetsYasa-Sheets”” Equipped with a Multilayer Coating Equipped with a Multilayer Coating

The Yasa-sheet, invented by S. Shiratori of Keio

University, is equipped with a multilayer film and

contains an enzyme (extracted from bamboo) that

controls the ethylene concentration and such

extends the shelf-life of fruits and vegetables.

The product, sold by PLUSTO (Japan), received

the „Excellent Product Award“ of Nikkei in 2001.

Image and movie are taken from the PLUSTO website.


Metal Rubber, fabricated by layer-by-layer assembly by the company NanoSonic in Blacksburg, Virginia, is claimed to

combine low modulus (about 10 MPa) with almost metal-like electrical conductivity (sheet resistance as low as 0.1 / .

Temperature resistance up to 160 °C, highly resistant against aggressive solvents. The properties are maintained over

millions of cycles.

Product information from NanoSonic. Photo from: Popular Science, August 2004, page 36

Metal Rubber™ (NanoSonic Inc.)



Surfaces of Any Kind and Any Shape ?Surfaces of Any Kind and Any Shape ?Here is an example of hollow multilayer capsules made by Here is an example of hollow multilayer capsules made by templating templating on colloidal particleson colloidal particles

First, deposit polyelectrolytes on a micron-sized colloid

Then dissolve the colloid core

E. Donath, G. B. Sukhorukov, F. Caruso, S. A. Davis, and H. Möhwald, Angew Chem Int Ed 37, 2202-2205 (1998).


Multilayers of PAH and PSS on 13nm Colloids

Easy Access to Stable (Bio)functional Nanoparticles

Grégory Schneider and Gero Decher, Nano Lett., Vol. 4, No. 10, 2004, 1832-1839


Can be made on ANY surface

Control of composition

Di erent colors representdi erent functionalities

Examples: polymers, proteins,nanoparticles, …

Components can be fixed ormobile

Porosity control, …

Molecular scale (0.5 to 10 nm)

nanoscale50 nm

to

macroscale5 mm


LbL - the ONE does it ALL nano-coating solution

• Broadness, Integrateability, Adaptability, ...

• Choice of components (bio/macro)molecules, colloids, ...

• Choice of surfaces (any size, any shape)

• Choice of solvent (water, others are possible)

• Patternability

• Quality control (chemical purity, homogeneity, reproducibility)

• Overall device yield

All competitive techniques are limited (if not fail)with respect to several items of this list (in comparison with LbL)

However, LbL can easily be integrated with most competitive techniques !

pseudo - inconvenience of LbL:

• Number of proccessing steps

- increases with number of components

- increases with numbers of layers

- BUT it just means adding a beaker (baths) to the deposition chain

Technological advantages over competitive techniques:

(Langmuir-Blodgett, self-assembled monolayers, covalent coupling,grafting from, grafting to, spin coating, ...)


0

20

40

60

80

100

120

0

100

200

300

400

500

1990 1992 1994 1996 1998 2000

number of publications / year

total number of publications

publication year

Source: P. Bertrand, A. Jonas, A. Laschewsky and R. Legras

Macromol. Rapid. Commun. 21 (2000), 319-348

More Symposia: 223rd ACS National Meeting

Orlando, Florida, April 7-11, 2002

226th ACS National Meeting

New York, Sept. 7-11, 2003

227th ACS National Meeting

Anaheim, Ca. March 28-April 1, 2004

The first symposium on

Polyelectrolyte MultilayersWas held on occasion of the

American Chemical Society National Meeting - Colloid DivisionSan Francisco, Ca., March 26-31, 2000

Joseph B. Schlenoff, Gero Decher, organizers

The Field is Rapidly ExpandingThe Field is Rapidly Expanding


A list of recent reviews, newsletters and books:

(1) Decher, G., Layered Nanoarchitectures via Directed Assembly of Anionic and Cationic Molecules; in: Comprehensive

Supramolecular Chemistry, Vol. 9, "Templating, Self-Assembly and Self-Organization"

(Sauvage, J.-P. and Hosseini, M. W., Eds.), Pergamon Press: Oxford, 1996; 507-528.

(2) Decher, G., Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites, SCIENCE 1997, 277, 1232-1237.

(3) Decher, G.; Eckle, M.; Schmitt, J.; Struth, B., Layer-by-Layer assembled multicomposite films. Curr. Opinion Coll. &

Interf. Sci. 1998, 3, 32-39.

(4) Bertrand, P.; Jonas, A.; Laschewsky, A. and Legras, R., Ultrathin polymer coatings by complexation of

polyelectrolytes at interfaces: suitable materials, structure and properties. Macromol. Rapid. Commun. 2000, 21, 319-

348.

(5) Paula T. Hammond, Recent explorations in electrostatic multilayer thin film assembly. Curr. Opinion Coll. & Interf. Sci.

2000, 4, 430-442.

(6) Michael Freemantle, C&EN: Science & Technology - Polyelectrolyte Multilayers, Chemical & Engineering News, May

6 (2002), Vol. 80 (18), pp. 44-48

(7) Jessica Gorman, Layered Approach: A simple technique for making thin coatings is poised to shift from curiosity to

commodity, Science News, Week of Aug. 9, 2003; Vol. 164, No. 6

(8) Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-

VCH: Weinheim, 2003; 524 pages.


Multilayer Thin Films -

Sequential Assembly of Nanocomposite Materials

Decher, G. / Schleno , J. B. (eds.)

With a Foreword by Jean-Marie Lehn

Wiley-VCH, Weinheim, Germany, 2003, 524 pages

ISBN 3-527-30440-1

Chapters from: G. Decher (Inst. Charles Sadron), V. Kabanov (MoscowState University), J. F. Joanny (Institut Curie),

J. Schleno (Florida State University), M. Rubner (MIT),

T. Kunitake and Y. Lvov (RIKEN and Louisiana State University), A.Jonas (University of Louvain-la-Neuve),

N. Kotov (Oklahoma State University), J. Fendler (Potsdam, USA), P.Hammond (MIT), J. Shen and X. Zhang (Jilin University), F. Caruso andG. Sukhorukov (MPI-KG),

H. Möhwald (MPI-KG), D. Kurth and R. v. Klitzing (MPI-KG and TUBerlin), B. Tieke (University of Cologne), R. Claus (Viginia StateUniversity), and M. Brüning (Michigan State University)

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