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Assembly of Nanoparticles in Multiscales and Multidimensions - - PowerPoint PPT Presentation

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Assembly of Nanoparticles in Multiscales and Multidimensions (Multiscale Architecturng): Platform for Convergence Technology Mansoo Choi Global Frontier Center for Multiscale Energy Systems School of Mechanical and Aerospace Engineering,

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Assembly of Nanoparticles in Multiscales and Multidimensions (Multiscale Architecturng): Platform for Convergence Technology

Mansoo Choi Global Frontier Center for Multiscale Energy Systems School of Mechanical and Aerospace Engineering, Seoul National University, Seoul 151-742, Korea Email : mchoi@snu.ac.kr

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Why Multiscale ?

Multiscale approach integrating nano, micro and macroscales is needed to optimize the process.

Example: Solar and Fuel Cells

  • Energy conversion and transfer in solar and fuel

cells are multiscale phenomena

  • Energy carriers: photon, electron, exciton, plasmon,

molecule ion, phonon

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Optical path length enhancement

path length enhancement Atwater et al., Nature Materials (2010)

Plasmonic solar cell utilizes multiscale metal nanoparticle patterns to enable physically thin but optically thick cells to maximize light trapping

Cui et al., Nano Letters, 2010 Polman and Atwater, Optical Society of America, 2010

Multiscale plasmonic solar cells

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Surface Enhanced Raman Scattering (SERS) based on nanoparticle patterns

Mu et al. (2010), Nanotechnology., 21: 015604

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Nanoparticles: Building Blocks for Nanotechnology

l Nanoparticles have long been conceived as the fundamental building blocks for realizing nanotechnology Nanoparticles Nanotechnology Multiscale Architecturing

It remains challenging for a controlled way of nanoparticle assembly in multiscales and three dimensions.

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Some of Existing Nanoscale Patterning Methods

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Liu et al., Nature Materials, 2007 Koh et al., Nano Letters, 2011

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Micro-contact Printing (parallel but , uniform contact

problem, difficulty in 3D architecturing) : Whitesides group

Wilbur et al., Nanotechnology, 1996

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Capillary Force Assembly Cui et al., Nano Lett., Vol. 4, No. 6, 2004

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

From traditional gravure printing to high- resolution particle printing

KRAUS et al. , Nature Nanotechnology, 2, 570 (2007)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Particle structures printed on flat Si substrates.

KRAUS et al. , Nature Nanotechnology, 2, 570 (2007)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Need to develop Cost-effective High-throughput Nano- Assembly Technique:

Multiscale, multidimensional assembly, Parallel, Atmospheric, Nanoscale resolution, Large surface area, Independent of substrates and materials

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Our Method : Ion Assisted Aerosol Lithography( IAAL)

(Nature Nanotechnology(2006), Patents Registered in Korea and USA)

l Charged aerosol nanoparticles are precisely positioned on the desired location via ion- induced focusing electrostatic field. l This is a parallel atmospheric process ensuring nanoscale resolution on large surface area.

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Aerosol positioning and assembling of nanoparticles

  • As particle size decreases, thermal driven random

Brownian motion of nanoparticles becomes significant.

particle

  • f

t coefficien Diffusion D time t t coefficien friction f e Temperatur T constant Boltzmann k Dt f Tt k x

B B

_ : , : _ : , : , _ : 2 2

2

= = > <

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Aerosol Positioning and assembling of nanoparticles

  • Precise positioning of nanoparticles is required for nanoscale

assembly of nanoparticles. Suppression of thermal motion of nanoparticles is necessary. Electrostatic force is utilized to suppress random Brownian particle deposition .

Particle size D Brownian random movement at 20°C in 1 second 1μm 7μm 100nm 37μm 10nm 320μm 1nm 3200μm (= 3.2mm)

/sec) (cm2

  • 7

10 2.77´

  • 6

10 75 . 6 ´

  • 4

10 24 . 5 ´

  • 2

10 5.14´

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Seoul National University

Global Frontier Center for Multiscale Energy Systems Charge Accumulation

  • n Surface of PR

PR Strip Ion( ) and Charged Aerosol ( ) Nanoparticle Injection

  • 4 kV

Focused Deposition

  • 4 kV

Equi-Potential Line acting as a nanoscopic electrostatic lens Si

Si

Ion Assisted Aerosol Lithography

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 17

Through DMA, we select 10 nm silver nanoparticles.

1mm

75nm

1mm

75nm 230nm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 18

200nm 135nm

Nanoscopic electrostatic lenses

▶without ion injection

200nm 135nm

▶w/ ion injection (4lpm)

Ion mobility vs particle mobility

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

100nm

100nm

75nm 35nm

100nm 100nm 100nm

Focusing effect with the increase of ion flow rates

(Nature Nanotechnology,1, 117, 2006)

0lpm 3lpm 4lpm 6lpm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Simulation of Electrodynamic Focusing of Charged Aerosols

W E B D p p

F F F F dt v d m + + + =

D

F

: Fluid Drag Force

B

F

: Brownian random Force

E

F

: Electric Force

W

F

: Van der Waals Force

  • Particle Trajectories : Langevin Equation
  • Electric Field : COMSOL CODE
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Seoul National University

Global Frontier Center for Multiscale Energy Systems

A. No ion injection B. With ion injection, N2 3lpm C. With ion injection, N2 6lpm

Simulation Results (Journal of Aerosol Science,

Nov., 2007)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Electrospray of nanoparticle suspension

(Applied Physics Letters, 94, 053104, 2009)

Patterning of nanoparticles that were already made

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 23

(a) 5mm (b1) 5mm

Ion shower 30min, Deposition 30min, Without neutralizer

Vs=- 4kV

30nm Polystyrene nanoparticles

(b) 5mm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 24

Results – Charge Distribution

With neutralizer Without neutralizer

Geometric mean : 3.2 GSD : 1.88 Geometric mean : 134 GSD : 1.49

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 25

Inertial effect of 10 nm particles: Too high charge, too high velocity

(a) (b)

Ion shower 30min, Deposition 30min, W/O neutralizer Ion shower 30min, Deposition 30min, W/ neutralizer Vs=-4kV Vs=-4kV

<3um line pattern>

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 26

Results – Effects of neutralizer 2

(a2) 5mm (b2) 5mm

Ion shower 30min, Deposition 30min, W/O neutralizer Ion shower 30min, Deposition 30min, W/ neutralizer Vs=-4kV Vs=-4kV

<2um circle pattern>

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Protein Patterning(Human IgG)(Small, 7, 1790, (2011))

<scale bar = 10 mm>

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Protein Patterning – nanoscale, parallel method

(Small, 2011)

<scale bar = 1 mm>

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Protein Patterning in microfluidic channels

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Do we need resist prepatterning ? Can we eliminate this process ? Solution : Nanoparticle Focusing Mask (Small ,Vol. 6, p 2146, 2010)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Nanoparticle Focusing Mask

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

(D) 600 nm (C) 400 nm 4kV, 2lpm

N2 ion flow rate of 2 l/min AFM image Gaussian Profile

Nanoparticle Focusing Mask : Silicon Nitride Mask

4 mm à 0.4 ~ 0.6 mm

4 mm aperture mask

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

(C) 2 lpm (D) 4 lpm (B) 1 lpm (A) 0.5 lpm

Silicon nitride mask

1000 nm 500 nm 300 nm 150 nm 4 mm

4 mm à 0.15 ~ 1 mm

Size Control by Ion Flow Rate

(Small ,Vol. 6, p 2146, 2010)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Substrate Substrate

Schematic of stencil translation Control the space between patterns by sequential deposition

Sequential Deposition

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

80 nm

Focusing Mask with 500 nm line openings (manufactured by e-beam lithography) 500 nm

Focusing Nano-Mask

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Focused patterning on thick non-conducting substrates

400 mm 200 mm 50 mm opening 50 ×50 mm2

  • pening

50 mm opening 7 mm 10 mm 12×12 mm2 10 mm 2 mm opening 420 nm

Patterning of electrosprayed 30 nm PSL particles on thick glass(~ 0.7 mm) Patterning of electrosprayed 100 nm PSL particles on a flexible PET film (thickness ~ 0.1 mm)

400 mm 50 ×50 mm2

  • pening

50 mm opening 10 mm 12×12 mm2

( Small ,Vol. 6, p 2146, 2010 )

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Is it possible to assemble nanoparticles in three dimensions using IAAL(Ion Assisted Aerosol Lithography) ?

Nanoparticles Nanotechnology 3 Dimensional Assembly

  • f Nanoparticles ?
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Seoul National University

Global Frontier Center for Multiscale Energy Systems 38

Scheme for 3D Assembly of Nanoparticles

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 39

Time Dependent Growth of 3D Nanoparticle Structures Arrays (Presented at 2008 AAAR Conference , Orlando, Abstract book, 2D. 04.)

T=4 min T=10 min T=40 min T=90 min T=10 min T=20 min T=90 min T=120 min Scale bar : 1.5 mm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 40

Numerical Calculation of Particle Trajectory and Deposition

(a) (b) (c) (d)

Scale bar : 500 nm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Growth of Nanoparticle Structure

(Nano Letters, “Three dimensional assembly of nanoparticles from charged aerosols”, Vol.11, 119, 2011)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 42

Array of 3D nanostructure of nanoparticles

(a) (b) (c)

35 nm 220 nm 200 nm 100 nm PR Substrate

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 43

Four-leaf clover like 3D nanostructure array of nanoparticles (Nano Letters, vol. 11, 119)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems 44

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

(a) 3D Nanoparticle Structures within Micron Scale SiO2 Patterns ( 2008 AAAR Conference, Orlando ) (c) (d) (b)

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Asymmetric and Isolated Nanoparticle Structures (Nano Letters, 2011)

(a) (b) (c)

Pattern width : 500 nm

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Applications of Aerosol Assembly

  • f Nanoparticles

: Nanodevices based on 3D nanoparticle array.

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Summary

l Aerosol engineering plays an important role for multiscale architecturing which can be a platform for convergence technology. l “Ion Assisted Aerosol Lithography (IAAL)” is a general methodology of multiscale 3D architecturing: parallel, large area, nanoscale resolution on the surface regardless of metallic or dielectric or flexible film or thick glass at atmospheric pressure. l Various nanodevices based on 3D nanoparticle assembly such as 3D gas sensors, 3D SERS, 3D solar cells were demonstrated.

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Seoul National University

Global Frontier Center for Multiscale Energy Systems

Acknowledgements

Sponsor: Korean Ministry of Science, ICT and Future Planning,