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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
4Institut 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
5Institut Charles Sadron
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.
6Institut Charles Sadron
Pierre Schaaf, Gero Decher, Jean-Claude Voegel
La Recherche, No. 389, SEPT. 2005, 56-58
The multilayer films that can do everything . . .
7Institut Charles Sadron
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.
8Institut Charles Sadron
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)
9Institut Charles Sadron
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.
10Institut Charles Sadron
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
. . .
. . .
. . .
Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-VCH: Weinheim, 2003; 524 pages.
11Institut Charles Sadron
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.
12Institut Charles Sadron
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. . .
Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-VCH: Weinheim, 2003; 524 pages.
13Institut Charles Sadron
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
14Institut Charles Sadron
A bit of History (2):A bit of History (2):
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)
409 ISI-Citations (as of January 2006)
Adsorption
Polyanion
Adsorption
Bola-dication
Number of Layers
15Institut Charles Sadron
A bit of History (3):A bit of History (3):
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)
729 ISI-Citations (as of January 2006)
Adsorption
Polyanion
Adsorption
Polycation
16Institut Charles Sadron
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+
17Institut Charles Sadron
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)
193 ISI-Citations (as of January 2006)
18Institut Charles Sadron
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).
20Institut Charles Sadron
Automatic Layer Deposition Using a Automatic Layer Deposition Using a ““DippingDipping”” Robot Robot
Automated deposition device, R&K Ultrathin Organic Film Technology, Berlin, Germany
21Institut Charles Sadron
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
22Institut Charles Sadron
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)
190 ISI-Citations (as of January 2006)
23Institut Charles Sadron
Large surfaces are coated by spraying
Albert Izquierdo and Claudine Porcell
24Institut Charles Sadron
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
25Institut Charles Sadron
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
26Institut Charles Sadron
• 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
Photo courtesy of L. Winterton (CIBA-Vision), presented on occasion of the 223rd ACS National meeting April 7-11, 2002.
27Institut Charles Sadron
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.
28Institut Charles Sadron
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.
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
29Institut Charles Sadron
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
30Institut Charles Sadron
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
31Institut Charles Sadron
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.
33Institut Charles Sadron
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.)
Partially based on US Patent US 520 8111, G. Decher & J.-D. Hong
34Institut Charles Sadron
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).
35Institut Charles Sadron
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
36Institut Charles Sadron
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
37Institut Charles Sadron
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, ...)
38Institut Charles Sadron
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
39Institut Charles Sadron
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.
40Institut Charles Sadron
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)
For more information: