“La deposition couche-par-couche :
Les millefeuilles moléculaires à tout faire”
Traitements de surfaces des matériaux souples : Quels procédés pour quelles applications ?
Journée ECRIN-Traitements de Surfaces et ECRIN-Agroalimentaire, Grenoble, le 13 octobre, 2005
Layer-by-Layer Assembly (LbL):
An Enabling Technology for the
Nanofabrication of Multicomposite
Films on Solvent Accessible
Surfaces.
Gero Decher / Institut Charles Sadron
Pierre Schaaf, Gero Decher, Jean-Claude Voegel
La Recherche, No. 389, SEPT. 2005, 56-58
Institut Charles Sadron
New Laboratory 2006
Integration into the Materials Science Campus / Cronenbourg
The Strasbourg Multilayer Team :
Chemistry (CNRS, UPR22)
Physics (CNRS, UPR22)
Biomedicine (INSERM, U595)
G. Decher
P. Schaaf
J.-C. Voegel
Ph. Mesini
O. Felix
V. Vivet
A. Izquierdo
S. Ono
B. Saulnier
M. Eckle
D. Pointu
G. Schneider
B. Struth
V. Ball
G. Ladam
P. Nagankam
F. Boulmedais
E. Hübsch
N. Laugel
M. Michel
C. Porcell
P. Schwinte
...
C. Picart
N. Jessel
Ph. Lavalle
F. Cuisinier
J. Ogier
A. Klucsar
J. Chluba
B. Senger
L. Richert
...
Differences between chemistry in bulk and at interfaces
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 monolayer
corresponds 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 1.5 mg of material per 1 m2.
• Less than 0.02 mg for chemical analysis and physical characterization
Advantage: We only need tiny amounts from colleagues doing synthesis
For years, surface modification
has been difficult.
Now, functional surfaces and
objects can be built to order
using
Layer-by-Layer deposition
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-toorder" fashion. It exceeds simple self-organization under
equilibrium conditions by making it possible to arrange
many different materials at will with nanoscale precision.
Ready for a paradigm change in
surface functionalization ?
Can we dream to functionalize any surface with any ligand,
independent of the substrate material, its shape or its size,
by adsorption from aqueous solutions ?
Toward a paradigm change in surface functionalization
Drawbacks of direct covalent coupling (grafting):
•
•
•
•
•
optimisation of conditions for each ligand/surface combination
side-products of the reaction cannot be removed
very difficult to get a detailed chemical composition of the surface
sometimes difficult to vary the density of functional groups
organic solvents or harsh conditions are frequently required
A modular approach: 1. Coupling, 2. Adsorption
F
F
F
F
+
+
+
+
-
-
-
-
-
-
-
-
-
Advantages of a two step (modular) approach:
1)
•
•
•
•
classical chemical coupling of a ligand to a polymer in solution
routine analysis of reaction products
option to separate reaction products
degree of substitution can be controlled
quality control before deposition
2)
•
•
•
deposition of the polymer on the surface
similar to identical deposition conditions for different ligand/surface combinations
mild deposition conditions from aqueous solutions
characterisation can be carried out on separate samples, even on different substrates
Schematic of the Layer-by-Layer Deposition Process
Simplified “molecular”
molecular”
picture of the first two
adsorption steps depicting
film deposition as starting
with a positively charged
substrate. Counterions are
omitted for clarity.
Polyion conformation is
highly idealized and layer
interpenetration is not
shown in order to better
represent the surface
charge reversal with each
adsorption step.
G. Decher, Science 277, 1232-1237 (1997)
Automatic Layer Deposition Using a “Dipping” Robot
Automated deposition device, R&K Ultrathin Organic Film Technology, Berlin, Germany
The process is (in general) very reliable, the film thickness
being precisely controlled by the ionic strength
PEI/(PSS/PAH)5 on quartz from x M NaCl
automated device; no intermediate drying
300
0.15
300
0.14
280
0.14
280
260
0.13
220
0.11
200
0.10
180
160
0.09
260
0.13
240
0.12
220
0.11
200
0.10
180
160
0.09
140
0.08
140
0.08
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0.4
0.6
0.8
cNaCl
D [Å]
A @ 226 nm
y = m1 + m2*m0
m1
m2
Chisq
R
Value
0.054
0.061
6.8405e-06
0.99822
1.2
1.4
1.6
m1
m2
Chisq
R
Value
67
146
243.12
0.98912
D [Å]
A @ 226 nm
y = m1 + m2*m0
Error
0.002
0.003
NA
NA
1.0
cNaCl
y = m1+m2*m0
Error
15
15
NA
NA
y = m1+m2*m0
m1
m2
Value
0.059
0.063
Error
0.006
0.006
m1
m2
Value
74
150
Error
1
1
Chisq
4.3167e-05
NA
R
0.98951
NA
Chisq
1.151
NA
R
0.99995
NA
D [Å]
240
0.12
A @ 226 nm
0.15
D [Å]
A @ 226 nm
PEI/(PSS/PAH)5 on quartz from x M NaCl
manual dipping; dried after every layer
Some polyions already “multilayered”, here we use PSS and PAH
SO3OSO3- Na+
N
NH
SO2
SO3- Na+
O- Na+
NH+ •
O
O
S
HO3S
NH
HO3S
HN
N
N
CO2Na+
OH
NaPSS
PVS
NH3+ Cl-
PAZO
S+
Cl -
PAPSA
SPAN
PTAA
PAMPSA
+ H
+
N
Cl -
NH2
N
+
N
N
R
H2N
HN
N+
N
I-
N
S+
Cl HN
NH2
PSMDEMA
PAH
Pre-PPV
PDDA
PMPyA
R-PHPyV
PEI
Inversion of surface charge with deposition of each layer
40
PAH
Zeta Potential [mV]
Adsorption of polycations
poly(ethylene imine)
imine) (PEI) and
poly(allyl
poly(allyl amine) (PAH) renders the
surface positively charged. The
deposition of poly(styrene sulfonate)
sulfonate)
(PSS) yields a negative surface charge.
Similar measurements were also
obtained from other groups.
PEI
PAH
PAH
PAH
PAH
20
0
-20
PSS
PSS
PSS
PSS
PSS
-40
bare SiO surface
2
0
5
10
15
20
25
30
35
40
For a theory of surface charge
inversion see M. Castelnovo and J. F.
Joanny, Langmuir 16(19), 7524-7532
(2000) and for a mechanism of
multilayer formation see J. B.
Schlenoff and S. T. Dubas,
Macromolecules 34(3), 592-598
(2001).
Number of Measurement
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
Creating New Film Architectures is: SIMPLE !
At least 2 oppositely charged
(or otherwise interacting)
molecular species are required.
If the 2 solutions yield a
precipitate upon mixing,
chances for “multilayering”
multilayering” are
excellent.
Adding more “beakers”
beakers” leads
to periodic or non-periodic
multilayer architectures as
defined by the deposition
sequence.
Typical concentrations:
0.1 to 20 mg/ml
Typical adsorption times:
20 seconds to 1 hour
10
7
10
5
8.0 10-6
7.0 10
-6
6.0 10
-6
5.0 10
-6
n
Scattering Length Density [Å-2]
Reflected Intensity (Neutron)
From Neutron Reflectivity Curves:
Number of Deuterated Layers, Layer Positions and Layer Profiles
10
10
3
1
10-1
10-3
10-5
0
0.02
0.04
0.06
Qz [Å-1 ]
0.08
0.1
4.0 10-6
3.0 10
-6
2.0 10
-6
1.0 10
-6
0.0 10
0
0
500
1000
1500
2000
2500
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
15 min. / layer
6 sec. / layer
50 -150 times faster
A. Izquierdo, S. S. Ono, J.-C. Voegel, P. Schaaf, and G. Decher, Langmuir 2005, 21, 7558-7567
New Applications require Substrate-Free Membranes
Dr. Shoko Ono
Functional layer
Multilayer formed via
electrostaticinteraction
pH 2 => 7
pH responsive layer
Multilayer formed via
hydrogen-bonding
5 mm
4 mm
Self-Standing
Polyelectrolyte
Multilayer Film
Release of the Membrane from the Substrate
n = 20
n = 80
PEI/(PAA/PEG)9/PAA/(PAH/PSS)n
Which Factors Control Release ?
2) Chemical Composition of the Upper Layer
PEI (PAA/PEG)9PAA (PAH/PSS)12 (PAH/Clay)20
Clay Platelets
pH 2
stiff
24 mm
Neutral pH
Photo in Milli-Q water
Mechanical Reinforcement
Barrier Layer
(B. Struth, M. Eckle, G. Decher, R. Oeser, P. Simon, D. W. Schubert, and J. Schmitt
Europ. Phys. J. E 6 (5), 351-358 (2001).
Can be made on ANY surface
Control of composition
Dierent colors represent
dierent functionalities
Examples: proteins, factors,
nanoparticles, …
nanoscale
50 nm
to
Components can be fixed or
mobile
Porosity control, …
macroscale
5 mm
Molecular scale (0.5 to 10 nm)
"The nature of a biomaterial surface governs the processes
involved in biological response."
B. D. Ratner, A. B. Johnston and T. J. Lenk,
J. Biomed. Mater. Res., Vol. 21, (1987), 59-89.
Motivation for Research
• Human benefit
Making available medical treatments and devices
for improving the quality of life
• Economic reasons
The medical device industry has yearly sales of at
least US $ 100 billion, worldwide (1999).
A modular approach: 1. Coupling, 2. Adsorption
F
F
F
F
+
+
+
+
-
-
-
-
-
-
-
-
-
Advantages of a two step (modular) approach:
1)
•
•
•
•
classical chemical coupling of a ligand to a polymer in solution
routine analysis of reaction products
option to separate reaction products
degree of substitution can be controlled
quality control before deposition
2)
•
•
•
deposition of the polymer on the surface
similar to identical deposition conditions for different ligand/surface combinations
mild deposition conditions from aqueous solutions
characterisation can be carried out on separate samples, even on different substrates
The Advantage of Synthesis Followed by Standardized Deposition:
Quality Control and Independence of Substrate
H
N
O
O
H
H
N
O
H
N
NH
H
N
O
O
H
O
S
N
O
NH+3 Br-
O
n = 220
NH
O
NH2
y=3
x=1
N-methyl-morpholine, H20 / CH3CN
4h, room temperature
H H
N
S
O
N
H H
Rather than optimizing the coupling chemistry for each ligand and each substrate individually, the combination
of solution coupling with a standardized deposition procedure represents an important competitive advantage.
A Photopatterned Multilayer with Biotinylated Polymer
and Fluorescently Labeled Streptavidin
A “me too” experiment underlining that LbL is capable of adressing problems similar
to the ones treated by e.g. classic coupling methods.
Decher, G.; Lehr, B.; Lowack, K.; Lvov, Y.; Schmitt, J., Biosensors and Bioelectronics 1994, 9, 677-684.
RGD - induced promotion of osteoblast binding to cationic surfaces
V. Vivet, Ph. Mesini with F. Cusinier, J.-C. Voegel
cell
RGD
Last layer PLL (poly-l-lysine)
NH
H3N
C O
O
HN
O C
N
H
C
C
O
H
N
O
C
N
H
C
O
H
N
C
OH
O
C
HO
O
HN
C
PLL
Spacer
H2N
NH
RGD
Last layer PLL-RGD
Film Architectures Allowing to Control the Access of Cells to
Neighboring Functional Layers: Tailored Bio-Interfaces
Monocytes accessing an embedded layer of Protein A, probably 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
TNF- secretion as a function of layer composition
Poly-L-Lysine
A
Poly-D-Lysine
B
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 single technology for
coating surfaces of any size and any shape ?
Surfaces of Any Kind and Any Shape?
Here is an example of hollow multilayer capsules made by templating on 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).
Polyelectrolyte - Charged Sphere Interaction in Theory
Rene Messina, Christian Holm and Kurt Kremer, Langmuir 2003, 19, 4473-4482
Equilibrium conformations of polyelectrolyte chains on small spheres
as a function of the strength of the specific van der Waals attraction
1) a single polyelectrolyte chain on an oppositely charged sphere
2) two oppositely charged polyelectrolyte chains
3) many polyelectrolyte chains ( (a) to (c) = increasing number of chains)
Powerfull Templates: Gold Nanoparticles (13.5 nm)
1.6
eff
Absorbance
Absorption
1.4
1.2
1.0
0.8
0.6
0.4
m
0.2
0.0
300
400
500
600
Wavelength
(nm)
Longueur
d'onde
(nm)
Advantages:
dispersion in water
plasmon band
reports of the surrounding medium
700
800
Spectroscopy vs. Electron Microscopy
0,30
520 nm
Absorbance
0,25
0,20
650 nm
0,15
0,10
0,05
0,00
300
400
500
600
Wavelength (nm)
700
800
Colorful Colloids
Excess of polycation
1:1 stoichiometry
Excess of colloids
Excess of polymer
must be removed
Flocculation
(worst case)
Incomplete surface
coverage
So, evaluation by the naked eye allows to quickly screen
a whole matrix of parameters or the ageing of samples
Multilayer deposition as observed by TEM
Redispersion of coated nanoparticles in the absence of agitation
Taken after deposition of layer #14 (corresponding to 27 centrifugation cycles)
Dilution factor 50-60 per cycle
Average recovery 95% per layer over 20 layers
A single aspiration/release in the tube at the very right
Reproducibility
Dissolution of the gold core with KCN: Empty Nanospheres
2 Au +
1
/2 O2 + H2O + 4 KCN 2 K[Au(CN)2] + 2 KOH
LbL is (analogous to) a chemical reaction !
Classic Synthesis
Reagent(s)
(atoms, synthons)
series of
reaction
steps
LbL - Deposition
Surface
(template)
series of
deposition steps
Product(s)
(typically single species)
Multilayer Film
(defined layer sequence)
Molecular scale
Nano (meso) scale
Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-VCH: Weinheim, 2003; 524 pages.
„Reagents“ for LbL Deposition
Reagents: polymers
colloids
biomacromolecules
small molecules
small & complex ions
linear
branched
(starshaped)
copolymers
tacticity
degree of polymerization
composition
monomer sequence
polymeric
metallic
oxidic
size
polydispersity
composition
surface functionality
proteins
polynucleotides
bioaggregates
...
...
...
Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials; Decher, G. and Schlenoff, J. B., eds., Wiley-VCH: Weinheim, 2003; 524 pages.
LbL - the ONE does it ALL nano-coating solution
Technological advantages over competitive techniques:
(Langmuir-Blodgett, self-assembled monolayers, covalent coupling,
grafting from, grafting to, spin coating, ...)
•
•
•
•
•
•
•
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
For years, surface modification
has been difficult.
Now, functional surfaces and
objects can be built to order.
Please ask us !
< decher@ics.u-strasbg.fr >
Thank you for your attention !
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, 319348.
(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., WileyVCH: Weinheim, 2003; 524 pages.
A presentation is too short to tell the whole story
Our book was the bestseller in the Wiley-VCH Materials Science series in 2003
Multilayer Thin Films - Sequential Assembly of Nanocomposite
Materials
Decher, G. / Schlenoff, J. B. (eds.)
With a Foreword by Jean-Marie Lehn
Wiley-VCH, Weinheim, Germany, 2002, 524 pages
ISBN 3-527-30440-1
Chapters from: G. Decher (Institut Charles Sadron), V. Kabanov
(Moscow State University), J. F. Joanny (Institut Curie), J. Schlenoff
(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 and G. Sukhorukov (MPI-KG), H. Möhwald
(MPI-KG), D. Kurth and R. v. Klitzing (MPI-KG and TU Berlin), B.
Tieke (University of Cologne), R. Claus (Viginia State University), M.
Brüning (Michigan State University)
The Field is Rapidly Expanding
The first symposium on
120
number of publications / year
Polyelectrolyte Multilayers
500
total number of publications
Was held on occasion of the
100
400
American Chemical Society National Meeting - Colloid Division
San Francisco, Ca., March 26-31, 2000
80
Joseph B. Schlenoff, Gero Decher, organizers
300
60
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
200
40
100
20
0
1990
0
1992
1994
1996
publication year
1998
2000
Source:
P. Bertrand, A. Jonas, A. Laschewsky and R. Legras
Macromol. Rapid. Commun. 21 (2000), 319-348