G. Decher P. Schaaf J.-C

“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 V. Ball C. Picart O. Felix G. Ladam N. Jessel V. Vivet P. Nagankam Ph. Lavalle A. Izquierdo F. Boulmedais F. Cuisinier S. Ono E. Hübsch J. Ogier B. Saulnier N. Laugel A. Klucsar M. Eckle M. Michel J. Chluba D. Pointu C. Porcell B. Senger G. Schneider P. Schwinte L. Richert B. Struth ......

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-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. ReadyReady forfor aa paradigmparadigm changechange inin surfacesurface functionalizationfunctionalization ?? 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” 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) on quartz from x M NaCl PEI/(PSS/PAH) on quartz from x M NaCl 5 5 manual dipping; dried after every layer automated device; no intermediate drying

0.15 300 0.15 300

0.14 280 0.14 280 260 260 0.13 0.13 D [Å] 240 240 D [Å] 0.12 0.12 220 220 0.11 200 0.11 200 A @ 226 nm A @ 226 nm A @ 226 0.10 180 0.10 180 160 160 0.09 0.09 140 140 0.08 0.08 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0.4 0.6 0.8 1.0 1.2 1.4 1.6 c c NaCl NaCl A @ 226 nm D [Å] A @ 226 nm D [Å]

y = m1 + m2*m0 y = m1 + m2*m0 y = m1+m2*m0 y = m1+m2*m0 Value Error Value Error Value Error Value Error m1 0.054 0.002 m1 67 15 m1 0.059 0.006 m1 74 1 m2 0.061 0.003 m2 146 15 m2 0.063 0.006 m2 150 1 Chisq 6.8405e-06 NA Chisq 243.12 NA Chisq 4.3167e-05 NA Chisq 1.151 NA R 0.99822 NA R 0.98912 NA R 0.98951 NA R 0.99995 NA Some polyions already “multilayered”, here we use PSS and PAH

SO - 3 O- Na+ - + N OSO3 Na NH NH+ • SO2 O O NH S SO - Na+ 3 HO3S HO3S HN N N

- CO2 OH Na+

NaPSS PVS PAZO PAPSASPAN PTAA PAMPSA

H NH S+ + 2 N N Cl - NH + Cl- + 3 N N H N + 2 Cl - R 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

Adsorption of polycations 40 PEI poly(ethylene imine) (PEI) and PAH poly(allyl amine) (PAH) renders the PAH PAH PAH PAH poly(allyl amine) (PAH) renders the surface positively charged. The 20 deposition of poly(styrene sulfonate) (PSS) yields a negative surface charge. Similar measurements were also 0 obtained from other groups.

For a theory of surface charge -20 inversion see M. Castelnovo and J. F.

Zeta Potential [mV] Zeta Joanny, Langmuir 16(19), 7524-7532 PSS PSS PSS PSS PSS (2000) and for a mechanism of -40 multilayer formation see J. B. bare SiO surface 2 Schlenoff and S. T. Dubas, Macromolecules 34(3), 592-598 0 5 10 15 20 25 30 35 40 (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” are excellent. Adding more “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 From Neutron Reﬂectivity Curves: Number of Deuterated Layers, Layer Positions and Layer Proﬁles

107 8.0 10-6

-6 105 7.0 10 ] -2 6.0 10-6 [Å n 3 10

5.0 10-6

101 4.0 10-6

3.0 10-6 10-1

2.0 10-6 Reflected Intensity (Neutron) Intensity Reflected 10-3 Scattering Length Density 1.0 10-6

-5 10 0.0 100 0 0.02 0.04 0.06 0.08 0.1 0 500 1000 1500 2000 2500 Q [Å-1 ] z 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 Self-Standing Multilayer formed via Polyelectrolyte electrostatic interaction pH 2 => 7 Multilayer Film pH responsive layer Multilayer formed via hydrogen-bonding

5 mm

4 mm 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 stiff

pH 2 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 Components can be ﬁxed or 50 nm mobile Porosity control, … to 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:

O O O O H H H N N N H NH N O H H O S N O + - O NH3 Br NH NH 2 n = 220 O x = 1 y = 3 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 O O HN H H C NC NC N C N C OH O C H H O O C HO O HN C NH H 2N PLL Spacer 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

1.4

1.2

1.0 eff 0.8 Absorption

Absorbance 0.6

0.4

0.2 m 0.0 300 400 500 600 700 800 LongueurWavelength d'onde (nm) (nm)

Advantages: dispersion in water plasmon band reports of the surrounding medium Spectroscopy vs. Electron Microscopy

0,30 520 nm 0,25

0,20 650 nm 0,15 Absorbance 0,10

0,05

0,00 300 400 500 600 700 800 Wavelength (nm) Colorful Colloids

Excess of polycation 1:1 stoichiometry Excess of colloids

Excess of polymer Flocculation Incomplete surface must be removed (worst case) 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

1 2 Au + /2 O2 + H2O + 4 KCN 2 K[Au(CN)2] + 2 KOH LbL is (analogous to) a chemical reaction !

Classic Synthesis LbL - Deposition

Reagent(s) Surface (atoms, synthons) (template) series of series of reaction deposi- steps tion steps

Product(s) Multilayer Film (typically single species) (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

linear tacticity branched degree of polymerization Reagents: polymers (starshaped) composition copolymers monomer sequence

polymeric size polydispersity colloids metallic oxidic composition surface functionality

proteins biomacromolecules polynucleotides bioaggregates

small molecules ...... small & complex ions . . .

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 ! < [email protected] >

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, 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. 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

120 number of publications / year The first symposium on 500 total number of publications Polyelectrolyte Multilayers 100 Was held on occasion of the 400 American Chemical Society National Meeting - Colloid Division 80 San Francisco, Ca., March 26-31, 2000 Joseph B. Schlenoff, Gero Decher, organizers 300

60 More Symposia: 223rd ACS National Meeting Orlando, Florida, April 7-11, 2002 200 226th ACS National Meeting 40 New York, Sept. 7-11, 2003 227th ACS National Meeting Anaheim, Ca. March 28-April 1, 2004 100 20

0 0 Source: P. Bertrand, A. Jonas, A. Laschewsky and R. Legras 1990 1992 1994 1996 1998 2000 Macromol. Rapid. Commun. 21 (2000), 319-348

publication year