electrochemical additive manufacturing of metal ...adv. mat. 29 (2017) 1604211 (review) 16 ......

Tomaso Zambelli, [email protected] of Biosensors and Bioelectronics, www.lbb.ethz.ch

electrochemical additive manufacturing of metal microstructures with the FluidFM

1

LBB and surface patterns at the micrometer scale

biomolecular micropatternsto direct cell growth

Vogt et al. Biomaterials 2005 26:2549Martinez et al. Lab Chip 2016 16:1663

microarraysfor sensing applications

Städler et al. Biointerphases 2006 1:142 200 µm 5 µm

outline

2

the FluidFM technology

electrochemical 2D patterning

electrochemical 3D printing

AFM (optical beam detection, OBD)

3

split‐diode photodetector

laser source

cantilever deflected because of the interaction of the tip with the surfacesurface

Meyer et al., Appl Phys Lett 1988 53:1045, OBD

Albrecht et al, J Vac Sci Technol 1990 8:3386, Si cantilevers

Binnig et al., Phys Rev Lett 1986 56:530, AFM

4

FluidFM: a force-controlled nanopipette

AFM cantilevers with a microchannel Simultaneous control of force + liquid flow

microfluidics + AFM FluidFM

Laser to measure deflection

Nano Lett. 9 (2009) 2501

5

Microchanneled AFM cantilevers

k ~ 0.2 - 2 N/m

Dr. Edin SarajlicSmartTip BV (NL) Cytosurge AG (CH)

Deladi et al, Appl Phys Lett 2004 85:5361

Berenschotet al, Small 2012 8:3823

FluidFM & single-cell manipulation

6by O. Guillaume-Gentil

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FluidFM for surface patterning: previous workinfluence of p, v, Fon nanoparticle deposition

cell-adhesive polymer patternsfor directed cell growth

PhD R Grüter

Nanoscale 5 (2013) 1097Langmuir 30 (2014) 7037

with PhD H. Dermutz

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local electrodeposition with FluidFM: principle

FluidFM as a local source of reactants for electrodeposition

first trials: Copper electroplating

Local reduction of metal ions

PhD L Hirt

RSC Advances 5 (2015) 84517

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2D ec-patterning: proof of concept with copper

large apertures (2-8 µm) and visual observation to find deposition parameters

(Ag QRE), 20 mV/s

(bottom view)

8 µm tipless probe, 50 mM CuSO4, p = 500 mbar


Cu dissolution

Cu plating

Cu platingH2 ev olution

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2D metal ec-deposition with force controlFluidFM is an AFM!ec-deposition and AFM topography with the same probe

In situ AFM(3D representation)

0 s

1 s

2 s

5 s

10 sPost-deposition SEM

20 µm

300 nm pyramidal probe, -0.6 V vs. Ag QRE, 50 mM CuSO4, p = 15 mbar, setpoint = 1 nN

0 s

1 s

2 s

5 s

10 s

Dep

ositi

on ti

me

2.7 µm


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ec-deposition: overpotential as ext. parameter

50 mM CuSO4, 15 mbar, 2 s approach time, 10 nN setpoint


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local electrografting with FluidFM:aryldiazonium salts

In situ AFM Ex situ SEM

300 nm pyramidal probeE = -0.7 V vs. Ag QRE3 mg/ml NBD · BF4

Substrate: ITOp = 0 mbarvTip = 4 µm/s (lines)

Thinnest lines ~150 nm

with Renaud CornutThomas BerthelotPascal Viel


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access to 3rd dimension!?!

In situ AFM(3D representation)

0 s

1 s

2 s

5 s

10 s

2.7 µm

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metal 3D printing yes, but limited resolution

current standard for additive manufacturing of metal: laser / e-beam melting

resolution limited (50-100 µm) by powder size and heat spreading

alternative techniques needed for the micrometer scale

Wikimedia

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additive manufacturing of metals at the micrometer scale: current developments

Adv. Mat. 29 (2017) 1604211 (review)

16

Meniscus-confined electroplating

Seol et al. Small 2015 11:3896

meniscus challenging automation difficult

EC-deposition reaction confined in the liquid meniscusbetween a glass micropipette and the substrate

pipette diameter: 15 µm

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ec 3D printing with FluidFM: protocol (1)

copper on gold

~40 nN

Adv. Mater. 28 (2016) 2311

PhD L Hirt

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«touching event»

copper on gold

~40 nN

Adv. Mater. 28 (2016) 2311

19


move up 0.5 µm (or away)

copper(!) on gold

~40 nN

not squeezing out, but voxel-by-voxel

Adv. Mater. 28 (2016) 2311

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control systemwith a bachelor student(!) S. Ihle

Adv. Mater. 28 (2016) 2311

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automation

10 µmdeflection monitored

user-defined shapeto be printed

30 µm

(2x speed)

Cu on ITO

«voxel by voxel» printing

Adv. Mater. 28 (2016) 2311

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copper micro-objects

overhangs / sideway deposition

layer-by-layer deposition

10 µm

10 μm

20 μm

10 μm5 μm

10 µm

5 µm

control over feature sizevia overpressure

4 7 10 13 16 mbar1

0 M

1 M

16 mbar1 mbar 20 min

15 min 80 min

20 min 30 min

Adv. Mater. 28 (2016) 2311

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fully dense, pure metal microstructures

with Alain Reiser, Prof . Spolenak (ETH D-MATL)

EDX of Cu pillars on AuCross section of a pillar500 nm

Adv. Mater. 28 (2016) 2311

W ORLD OF A PPLICA TIONS

3D PRINTING-METAL P RINT ING-

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Edgar HeppWabe KoelmansMiklos Mohos

zoom on two voxels

Signals during printing

= printed normally

= redundant point indesign

Visual feedback on desigSEM image of structure

Printing process monitoring and feedback on design

zoom on 2 voxels



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5 µm5 µm

pillar wall solid body

2D 3D1D

= voxel

10 µm


CO PPE R MICRO-OBJECTS



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5 µm

walls with ov erhang 90 degree ov erhang

• overhanging structures printed without support structures• 90 degree overhangs possible

2 µm





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wall with a window

2 µm

micro coil

10 µm 10 µm

cylinder



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conclusionsFluidFM for surface patterning localized electroplating &

electrografting mask-free patterning in-situ AFM imaging

FluidFM for 3D microfabrication «voxel by voxel» printing force feedback for automation

Outlook optimization other metals

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acknowledgements

Luca Hirt

Stephan IhleZhijian PanJohannes Braun

Raphael GrüterLiv ie Dorwling-Carter

Renaud CornutThomas BerthelotJérôme Polesel-MarisPascal Viel

Pablo Dörig, Pascal Behr, Mike Gabi


Alain ReiserRalph Spolenak Patrick Frederix

f unding

Martin LanzStephen Wheeler

János Vörös (head)

ScopeM, ETH ZürichZMB, Univ ersity of Zürich

electrochemical additive manufacturing of metal ...adv. mat. 29 (2017) 1604211 (review) 16 ......

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