Nanomaterials for bottom-up manufacturingNanomaterials for bottom-up manufacturing Jurriaan Huskens...
Transcript of Nanomaterials for bottom-up manufacturingNanomaterials for bottom-up manufacturing Jurriaan Huskens...
Nanomaterialsfor bottom-up manufacturing
Jurriaan Huskens
University of Twente, MESA+ Institute for NanotechnologyMolecular Nanofabrication group
Enschede, The Netherlands
General philosophy
Assembly: fundamental appliedPatterning:
fundamental
applied
3D nanostructures
flat stampsNIL patterning
printboards, multivalency, supramolecular nanolithography
patterned protein
constructions
Molecular printboards
CD monolayers on gold: infinite 2D receptor lattices:
M. W. J. Beulen, J. Bügler, M. R. de Jong, B. Lammerink, J. Huskens, H. Schönherr, G. J. Vancso, B. A. Boukamp,H. Wieder, A. Offenhäuser, W. Knoll, F. C. J. M. van Veggel, D. N. Reinhoudt, Chem. Eur. J. 2000, 6, 1176
CA: polarity: θadv = 55o
EIS: thickness: 2 - 3 nmXPS: bound sulfur: 65 %SIMS: molecular peaks: (M+Au)+
AFM: molecular order: 2.1 nmβ-cyclodextrin (CD)OHOH
OO
OH
7
Molecular printboards
Small guests at a CD monolayer:
K(M-1)
Δαsat
(°)
K(M-1)
ΔH(kcal mol-1)
TΔS(kcal mol-1)
OHFe 9.9⋅103 0.145 1.0⋅104 -6.1 -0.7
NH
O
2.6⋅104 0.179 3.0⋅104 -5.2 0.9
NH
O5.7⋅104 0.090 6.8⋅104 -5.9 0.7
00.020.040.060.08
0.10.12
0 20 40 60 80
Δα (º)
[guest] (μM)
M. R. de Jong,J. Huskens,D. N. Reinhoudt,Chem. Eur. J.2001, 7, 4164
General introduction to multivalency
Multivalency at interfaces:
Examples in Nature:
cell membrane interactionswith bacteria and viruses:
M. Mammen, S.-K. Choi, G. M. Whitesides, Angew. Chem. Int. Ed. 1998, 37, 2754
μCP on SAMs
Patterning with multiple multivalent molecules:
Em > 600 nm 500 < Em < 530 nm Simultaneous
Confocal microscopy images
60 μm
S. Onclin, A. Mulder, J. Huskens, B. J. Ravoo, D. N. Reinhoudt, Langmuir 2004, 20, 5460A. Mulder, S. Onclin, M. Péter, J. P. Hoogenboom, H. Beijleveld, J. ter Maat, M. F. García-Parajó, B. J. Ravoo, J. Huskens, N. F. van Hulst, D. N. Reinhoudt, Small 2005, 1, 242
Supramolecular materials
Supramolecular layer-by-layer assembly scheme using CD-Au colloids andadamantyl-functionalized dendrimers:
+
G5 dendrimer
Layer-by-layer assembly: G. Decher, Science 1997, 277, 1232O. Crespo-Biel, B. Dordi, D. N. Reinhoudt, J. Huskens, J. Am. Chem. Soc. 2005, 127, 7594
Supramolecular materials
Supramolecular building blocks for LBL assembly:
J. J. Michels, M. W. P. L. Baars, E. W. Meijer, J. Huskens, D. N. Reinhoudt, J. Chem. Soc., Perkin Trans. 2, 2000, 1914
OHOH
OO
OH
7
≡
≡
Molecular printboards:
J. Huskens, M. A. Deij, D. N. Reinhoudt, Angew. Chem. Int. Ed. 2002, 41, 4467; T. Auletta, B. Dordi, A. Mulder, A. Sartori, S. Onclin, C. M. Bruinink, C. A. Nijhuis, H. Beijleveld, M. Péter, H. Schönherr, G. J. Vancso, A. Casnati, R. Ungaro, B. J. Ravoo, J. Huskens, D. N. Reinhoudt, Angew. Chem. Int. Ed. 2004, 43, 369
+
Adamantyl dendrimers:
β-cyclodextrin
Supramolecular materials
Supramolecular building blocks for LBL assembly:
J. Liu, W. Ong, E. Román, M. J. Lynn, A. E. Kaifer, Langmuir 2000, 16, 3000
NaBH4HAuCl4DMSOCH3CNOHOH
OO
SH
7
+
O. Crespo-Biel, A. Juković, M. Karlsson, D. N. Reinhoudt, J. Huskens, Isr. J. Chem. 2005, 45, 353
Cyclodextrin gold nanoparticles:
TEM: diameter 2.8 ± 0.6 nm
Au
Supramolecular multivalent aggregation:
Supramolecular materials
Layer-by-layer assembly using CD-Au colloids and Ad dendrimers:SPR spectroscopy:
0.95
1.05
1.15
1.25
1.35
1.45
1.55
1.65
50 100 150 200 250 300 350 400 450 500
time (min)
Nor
m.In
tens
ity a
t Det
ecto
r
Solutions: 6.5 μM CD-Au (H2O)0.01 mM Ad-G5 (1 mM CD pH 2)
Rinse 1 mM CD pH 2Rinse H2O
O. Crespo-Biel, B. Dordi, D. N. Reinhoudt, J. Huskens, J. Am. Chem. Soc. 2005, 127, 7594
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
300 400 500 600 700 800λ (nm)
A
0
0.01
0.02
0.03
0 5 10 15 20# bilayers
A a
t 534
nm
Supramolecular materials
Layer-by-layer assembly using CD-Au colloids and Ad dendrimers:UV/Vis at glass substrates:
Quantitative interpretation possible:1 monolayer of particles per bilayer
0-18 bilayers
O. Crespo-Biel, B. Dordi, D. N. Reinhoudt, J. Huskens, J. Am. Chem. Soc. 2005, 127, 7594
Towards patterned LBL assemblies:
3D Nanofabrication:x,y: top-down patterningz: LBL assembly
3D Supramolecular materials
silicon
CD
silicon
silicon
inert SAM
CD inert SAM
CDpolymer template
Patterned SAMs:(μCP, NIL)
Patterned gold:(μCP+etching,
NIL+metal lift-off,sieve evaporation)
Patterned mask:(NIL)
silicon
Structures onpatterned
stamp:(μCP)
3D Supramolecular materials
Alternative: LBL on PDMS stamp followed by assembly transfer by μCP:
goldsilicon
silicon
PDMS
UV/O3
LBL assembly
CDs
O. Crespo-Biel, B. Dordi, P. Maury, M. Péter, D. N. Reinhoudt, J. Huskens, Chem. Mater. 2006, 18, 2545LBL in combination with μCP: J. Park, P. T. Hammond, Adv. Mater. 2004, 16, 520
3D Supramolecular materials
Patterned LBL assemblies by μCP:
1 2 3 4 5 6 7
5
10
15
20
heig
ht (n
m)
# bilayers
silicon
AFM height image(80 x 80 μm2)2 bilayers: 7 nm
AFM height image(60 x 60 μm2)4 bilayers: 14 nm
Assemblies are stable againstrinsing with competitive CD solutions
O. Crespo-Biel, P. Maury, M. Péter, B. Dordi, D. N. Reinhoudt, J. Huskens, Chem. Mater. 2006, 18, 2545
Directed nanoparticle assembly on NIL templatesNanofabrication scheme including NIL and directed nanoparticle deposition:
P. Maury, M. Péter, V. Mahalingam, D. N. Reinhoudt, J. Huskens, Adv. Funct. Mater. 2005, 15, 451
chemical template
topographical template
topographical template
chemical template
T>Tg
T≈Tg
Directed nanoparticle assembly on NIL templates
Improved particle deposition process: controlled wetting and capillary forces:
physical principle vertical NP deposition tool
Directed nanoparticle assembly on NIL templates
Particle adsorption in PMMA templates using vertical colloidal deposition:
P. Maury, M. Escalante, M. Péter, D. N. Reinhoudt, J. Huskens, Adv. Mater. 2005, 17, 2718
5 μm lines 600 nm lines
1 μm holes
10 μm 1 μm
1 μm1 μm
500 nm
1 μm
500 nm lines
Directed nanoparticle assembly on NIL templates
Particle adsorption on NIL-patterned SAMs using vertical colloidal deposition:
P. Maury, M. Escalante, M. Péter, D. N. Reinhoudt, J. Huskens, Adv. Mater. 2005,17, 2718
5 μm lines
200 nm lines
1 μm dots
1 μm dots
5 μm
1 μm
1 μm 1 μm
200 nm
NIL-patterned molecular printboards
NIL-patterned CD monolayers on SiO2:templates for multivalent supramolecular adsorption:
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
a)
1 mμ
b)
1 mμ
c)
1 mμ
AFM height: 0.9 nm 0.9 nm 2.8 nm(after polymer removal)
3D Supramolecular materials
Integration with layer-by-layer (LBL) assembly:
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
Lift-off
NPs: 2.8 nm CD Au
NPs: 60 nm CD SiO2
Lift-off
3D Supramolecular materials
AFM height image(30 x 30 μm2)2 bilayers: 6 nm
AFM height image(30 x 30 μm2)4 bilayers: 10 nm(15 process steps!)
NIL-patterned polymer masks for directed LBL: results:
NIL-patterned CD SAMs:
NIL-patterned CD SAMs followed by LBL, then polymer removal:
AFM height image(8 x 8 μm2)no bilayers: 2 nm(7 process steps)
3D Supramolecular materials
AFM height image(2.8 x 2.8 μm2)4 bilayers: 10 nmline width: 700 nm
AFM height image(4 x 4 μm2)2 bilayers: 5 nmline width: 700 nm
NIL-patterned polymer masks for directed LBL: results:
NIL-patterned CD SAMs followed by LBL:submicron patterns:
15 process steps !
J. Huskens, P. Maury, O. Crespo-Biel, M. Péter, D. N. Reinhoudt, Proceed. Instit. Mech. Engin. N: J. Nanoengin. Nanosys. 2006, 220, 157
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
3D Supramolecular materials
dot width: 200 nm 100 nm 50 nm
NIL-patterned polymer masks for directed LBL:results using an e-beam made master:
15 bilayers:37 process steps !!
SEM
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
500 nm500 nm 500 nm
500 nm 500 nm 500 nm
AFM
50 250150100 20010
20
30
40
50
Diameter (nm)
Hei
ght (
nm)
3D Supramolecular materials
NIL-patterned polymer masks for directed LBL:LBL with 60 nm CD SiO2 NPs:
SEM
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
2μm 2μm
2μm1
2
3
1-3 bilayers:height = n x 60 nm
AFM
3D Supramolecular materials
NIL-patterned polymer masks for directed LBL:LBL with 60 nm CD SiO2 NPs:
SEM
P. Maury, M. Péter, O. Crespo-Biel, X. Y. Ling, D. N. Reinhoudt, J. Huskens, Nanotechnology 2007, 18, 044007
2 bilayers on line and grid patterns
AFM
500 nm 100 nm
500 nm1 mμ
1 bilayer on dot patterns
3D Supramolecular materials
NIL-patterned polymer masks for directed LBL:LBL with 3 nm CD Au and 60 nm Fc SiO2 NPs:
5 m8
500 nm-5 0 5 10 15 20 25 30 35 40 45
0
500
1000
1500
2000
2500
3000
Thic
knes
s
Distance (micron)
L6 L5 L4 L3 L2 L1
L1 L2 L3 L4 L5 L60
50
100
150
200
250
300
350
400
450
thic
knes
s (n
m)
number of bilayerX. Y. Ling, I. Y. Phang, G. J. Vancso, D. N. Reinhoudt, J. Huskens, Int. J. Mol. Sci. 2008, 9, 486
Nanoparticle-substrate interface chemistry
Key question: What is the role of the interface chemistry on the assembly (order, reversibility) of large nanoparticles?Case study: 500 nm polystyrene NPs:
physisorption electrostatic host-guestX. Y. Ling, L. Malaquin, D. N. Reinhoudt, H. Wolf, J. Huskens, Langmuir 2007, 23, 9990
Nanoparticle-substrate interface chemistry
Key question: What is the role of the interface chemistry on the assembly (order, reversibility) of large nanoparticles?
Setup:
Movement of substrate
Evaporation
( ) Assembly ZoneA ( ) Solution ZoneB
Glass slideParticle convective flow
Tc
Temperature controller
X. Y. Ling, L. Malaquin, D. N. Reinhoudt, H. Wolf, J. Huskens, Langmuir 2007, 23, 9990
Physisorption: PS-COOH NPs on clean SiO2:
Assembly zone
Solution zone
Nanoparticle-substrate interface chemistry
Host-guest interaction: PS-CD NPs on CD SAMs with G1 Fc dendrimers:
Assembly zone
Solution zone
Nanoparticle-substrate interface chemistry
2 mμ
Host-guest interaction: PS-CD NPs on CD SAMs with G1 Fc dendrimers:
Assembly zone
Solution zone
competition by CD in solution
Nanoparticle-substrate interface chemistry
Summary
Assembly: fundamental appliedPatterning:
fundamental
applied
3D nanostructures
flat stampsNIL patterning
printboards, multivalency, supramolecular nanolithography
patterned protein
constructions
Acknowledgements
Molecular Nanofabrication group:Xing Yi Ling Dr. Olga Crespo-BielManon Ludden Dr. Pascale MauryProf. David Reinhoudt Dr. Maria Peter
Dr. Venkataramanan MahalingamProf. Bart Jan Ravoo
IBM Zurich, Switzerland: Dr. Laurent Malaquin, Dr. Heiko WolfTransducer Science and Technology, MESA+, University of Twente:Dr. Henri Jansen, Dr. Niels Tas, Prof. Miko ElwenspoekMaterials Science and Technology of Polymers, MESA+, University of Twente:Dr. Mark Hempenius, Prof. G. Julius Vancso
Financial support: