1

Self-Assembly for Nano and Micro Manufacturing

Babak A. Parviz

UC Berkeley, October 24th 2005

ParallelNanofabrication

3-D CircuitArchitectures

Low-costFabrication

Integration OfIncompatible

Processes

Nano-scaleElectronicDevices Complex

Systems WithMany

Elements

Self-Assembly

DNA~2-1/2 nm diameter

Things NaturalThings Natural Things ManmadeThings Manmade

Fly ash~ 10-20 µm

Atoms of siliconspacing ~tenths of nm

Head of a pin1-2 mm

Quantum corral of 48 iron atoms on copper surfacepositioned one at a time with an STM tip

Corral diameter 14 nm

Human hair~ 60-120 µm wide

Red blood cellswith white cell

~ 2-5 µm

Ant~ 5 mm

Dust mite

200 µm

ATP synthase

~10 nm diameterNanotube electrode

Carbon nanotube~1.3 nm diameter

O O

O

OO

O OO O OO OO

O

S

O

S

O

S

O

S

O

S

O

S

O

S

O

S

PO

O

The Challenge

Fabricate and combine nanoscale building blocks to make useful devices, e.g., a photosynthetic reaction center with integral semiconductor storage.

Mic

row

orl

d

0.1 nm

1 nanometer (nm)

0.01 µm10 nm

0.1 µm100 nm

1 micrometer (µm)

0.01 mm10 µm

0.1 mm100 µm

1 millimeter (mm)

1 cm10 mm

10-2 m

10-3 m

10-4 m

10-5 m

10-6 m

10-7 m

10-8 m

10-9 m

10-10 m

Visib

le

Nan

owor

ld

1,000 nanometers =

Infra

red

Ultra

violet

Micr

owav

eSo

ft x-

ray

1,000,000 nanometers =

Zone plate x-ray “lens”Outer ring spacing ~35 nm

Office of Basic Energy SciencesOffice of Science, U.S. DOE

Version 10-07-03, pmd

The Scale of Things The Scale of Things –– Nanometers and MoreNanometers and More

MicroElectroMechanical(MEMS) devices10 -100 µm wide

Red blood cellsPollen grain

Carbon buckyball

~1 nm diameter

Self-assembled,Nature-inspired structureMany 10s of nm

Self-Assembly

The complete “system”

Single cell

Complex (many elements)Three dimensionalNano-scale precisionCan span many orders of magnitude (interfacing with micro and macro)Self-reorganization and self-healing

A fundamentally different approach to making things.

Evolution of manufacturing

0-D

1-D2-D

Time

3-DBlacksmith

Assembly Line

SemiconductorMicrofabrication

SelfAssembly

Basic dilemmas• How do we make the parts?

– Chemical synthesis– Solid-state microfabrication

• How do we direct their self-assembly processes?– Specific covalent bonds– DNA programming– Genetically engineered polypeptides– Shape recognition– Directed surface tension forces

2

1 nm

10 nm

100 nm

1 µm

10 µm

100 µm

Self-assembled molecular electronics

Engineered DNA networks as templates for nanoelectronic circuits

Using genetically engineered polypeptidesto guide self-assembly

Self-assembling Si circuits on plastic

Self-assembled silicon networks1 mm

1 cm Hybrid silicon-organic systems

100 nm – 200 nm

9 Å

Easy integration with CMOSSub-nm control on potential landscape

What is a Self-Assembled Monolayer?What is a Self-Assembled Monolayer (SAM)?

head group

carbon chain

sulfur2-3

nm

head group

carbon chain

sulfur2-3

nm

STM courtesy of IBM

Molecules Forming SAM on Silicon Dioxide Surface

PO OHHO

PO OHHO

SiCl CH3

CH3 SiCl CH3

CH3

Anthryl dimethylchlorosilane Pyryl dimethylchlorosilane

Anthryl phosphonic acid Pyryl phosphonic acid

PYPA Self-Assembly•Can form mono or multilayer structures

•Form interesting crystal structure (important for crystalline monolayer)

• Competition between π-π stacking, hydrogen bonding and solvent interactions

Hin-Lap Yip, Hong Ma, Alex K.-Y. Jen, Jianchun Dong, Babak A. Parviz, “Two-Dimensional Self-Assembly of 1-Pyrylphosphonic Acid: Transfer of Stacks on Structured Surface”, submitted to the Journal of American Chemical Society

3

Fabrication Process of Electrodes

Si

Si

Oxidation

Si

Spincoating withPMMA

Si

Electron BeamLithography

Si

Liftoff

Si

Self-Assembly

Si

400 nm SiO2

70 nm PMMA

Cr/Au Evaporation

5/50 nm Cr/Au

1.5 nm ANPA

SEM Picture of the Fabricated Electrodes

Jianchun Dong, Babak A. Parviz, Hin L. Yip, Hong Ma, and Alex K-Y. Jen, “Construction and Electrical Characaterization of 0.9 nm Tall Channels Made via Pyryl Phosphonic Acid (PYPA) Self-assembly”, Proceedings of NSTI Nanotechnology Conference, v3, pp. 188-191, Anaheim CA May 8-12 2005

200 300 400 500 600 700 800 900 10000.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

Channel Length (nm)

I DS (n

A)

VGS = 0V VDS = 4V T = 300oK

1.5 2 2.5 3 3.5 410-14

10-13

10-12

10-11

10-10

10-9

10-8

VDS (V)

I DS (A

)

T = 300oKVGS = 0VL = 600 nm

Channel length dependence of current for PYPA devices

Parviz 2005

Temp. dependence of current for PYPA devices

AFM Picture

STM Picture

150 200 250 300 35010-18

10-16

10-14

10-12

10-10

10-8

Temperature (oK)

I DS (A

)

VGS

=0V VDS=4V (A)L = 400 nm

Fitting curve using Poole -Frenkel emission equation

Experimental data

-15 -10 -5 0 5 10 1510

-13

10-12

10-11

10-10

10-9

10-8

10-7

VG (V)

I DS a

t VD

S =

4V

(A)

330K320K310K300K290K280K270K260K250K240K230K

Gating the transport through the molecular system

220 240 260 280 300 320 340100

101

102

103

Temperature (oK)

On/

Off

Rat

io

Jianchun Dong, Hin L. Yip, Hong Ma, Alex K.Y. Jen, Babak A. Parviz, “Gated lateral charge transport in a self-assembled pyryl phosphonic acid molecular multi-layer with defined 2.5 nm step heights”, submitted to Journal of Applied Physics

-15 -10 -5 0 5 10 1510

-10

10-9

10-8

10-7

VGS (V)

µ h (cm

2 /Vs)

T = 230oKVDS = 4V L = 400 nm

10010-15

10-14

10-13

10-12

10-11

10-10

VDS (V)

I DS (A

)

VGS = 15VVGS = 10VVGS = 5VVGS = 0VVGS = -5VVGS = -10VVGS = -15V

T = 230oKL = 400 nm

VGS = -15V

VGS = -10V VGS = -5V

Gate voltage dependence of mobility

Parviz 2005

4

1 nm

10 nm

100 nm

1 µm

10 µm

100 µm

Self-assembled molecular electronics

Engineered DNA networks as templates for nanoelectronic circuits

Using genetically engineered polypeptidesto guide self-assembly

Self-assembling Si circuits on plastic

Self-assembled silicon networks1 mm

1 cm Self-assembling electronic components on DNA templates

C. Mao/B. A. Parviz (2005) 8 nm Palladium nanowire on DNA template

Platform for the Bottom-up self-assembly ofintegrated circuits

DNA Nanowire morphology study with AFM

John Lund, Jianchun Dong, Zhaoxiang Deng, Chengde Mao, and Babak Parviz, “DNA Networks as Templates for Bottom-up Assembly of MetalNanowires”, 5th IEEE Conference on Nanotechnology, Paper # TH-P2-5, Nagoya, Japan July 11-15, 2005

Electrical transport in DNA nanowires

Gold Pads (27 wires)

0

50

100

150

200

250

0 5 10

Voltage (V)

Cur

rent

(pA

)

120150180210240270300

T (K)_

DNA-directed self-assembly of nano photonic waveguides

Gain, G, through each QD Inter-dot coupling η

Pump light

SignalLinking chemistry

Quantum dots

substrateGain, G, through

each QD Inter-dot coupling η

Pump light

SignalLinking chemistry

Quantum dots

substrate

Hydroxyl groups on exposed surfaces of

PMMA trench

PMMASiO2/Si

OHOHOHOH

MPTMS

OOSi

SH

OSi

SH

OSi

SH

O OO

5’acrydite-DNA

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

Hydroxyl groups on exposed surfaces of

PMMA trench

PMMASiO2/Si

OHOHOHOHOHOHOHOH

MPTMS

OOSi

SH

OSi

SH

OSi

SH

O OO

5’acrydite-DNA

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

Biotin-cDNA

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

Streptavidin-QD

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

PMMASiO2/Si

Biotin-cDNA

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

Streptavidin-QD

SS S=O

H-N=O

H-N=O

H-N

OOSi

OSi

OSi

O OO

PMMASiO2/Si

Chia-Jean Wang, Lih Y. Lin, and Babak A. Parviz, “Modeling and Simulation for a Nano-Photonic Quantum Dot Waveguide Fabricated by DNA-Directed Self-Assembly”, IEEE Journal on Selected Topics in Quantum Electronics, v 11, n 2, March/April 2005, p 500-509

1 nm

10 nm

100 nm

1 µm

10 µm

100 µm

Self-assembled molecular electronics

Engineered DNA networks as templates for nanoelectronic circuits

Using genetically engineered polypeptidesto guide self-assembly

Self-assembling Si circuits on plastic

Self-assembled silicon networks1 mm

1 cm

5

Organic tools – Inorganic goals

Why me?

5 µm

200 nm

b

Proteins control hard tissue formation through nucleation, growth, compartmentalization, …… scaffolding, etc., leading to controlled architectures with hierarchical structures

Magnetic nanoparticles in bacteria

Hierarchically structured Dental tissues

Sponge spicules:natural optical fibers

Mammalian Enamel

Sarikaya et al. , PNAS, 1999

Xiaorong Xiang, Mary Lidstrom, Babak A. Parviz, “Microorganisms as Microelectromechanical Systems”, submitted to the ASME/IEEE Journal of Microelectromechanical Systems

A Look at Biology …

Weiner, et al., Science 2005

Phage display

P3

Constrained peptide

P6

M13Phage-Display

System

Principle: display at the N-terminus of phage M13 P3 protein

P3 copies per virion: 5Random segment size:

7 or 12 aa Primary clones:

1.9 x 109 (PhD12)Sequence space:

207 = 1.28 x 109

2012 = 4.1 x 1015

Cell surface display

Principle: cell surface display Within the active site loop of TrxA which is itself inserted within FliC

Flagella copies per cell: 10-15

Random segment size: 12 aa

Primary clones: 1.77 x 108

Sequence space: 2012 = 4.1 x 1015

FliTrx Cell-Surface

(Flagellar)Display System

GEPIGEPI – Genetically-Engineered Polypeptides for Inorganics

The Molecular Tool KitThe Molecular Tool Kit

Au Binders:GBP1:mhgktqatsgtiqs (14 AA)GBP2:ALVPTAHRLDGNM(14 AA)GBP3:LGQSGASLQGSEKLTNG(17 AA)GBP4:SEKLVRGMEGASLHPA(16 AA)GBP5:glndifeaqkiewh(14 AA)Ag-Binders:AgBP1:AYSSGAPPMPPF (16 AA)AgBP2NPSSLFRYLPSD (16 AA)AgBP3:SLATQPPRTPPV(16 AA)Pt-Binders:PtBP1:SVTQNKY(7 AA)PtBP2:HKVTLHN(7 AA)PtBP3:HGPDTRN(7 AA)Pd-Binders:PdBP1:SAGRLSA(7 AA)PdBP2:TLPNHTV(7 AA)PdBP3:INLSNRM(7 AA)ZnO Binders:CN122:LGSWGELLWQRQ(12 AA)CN173:YRDLLRSYRKRW(12 AA)CN177:HYANSIWALASQ(12 AA)Cu2O Binders:CN225: RHTDGLRRIAAR(12 AA)CN85: RTRRQGGDVSRD(12 AA)CN44:NTVWRLNSSCGM(12 AA)

Table – I:

AU

AG

Pt

pd

zno

cuxo

Materials of Interest:•Biocompatible MaterialsAl2O3, Stainless Steel., Ti-Alloys, HA

•Semiconductors:ZnO/ZnS, CdO/CdS, Si/SiGe ..

•Functional Substrates:Silica, Mica, Graphite, Calcite, ..

•Dielectrics/Ferroelectrics: ABO3•Magnetics: Metals, ferrites• ….

ALVPT

AHRLDGNM

AYSS

GAPP

MPP

F

HGPDTRN

YR

DLL

RS Y

RK

RW

RTRR

QG

GD

VSR

D

CSD

CSD

CSD

PD

PD

PD

Quartz Binders: (80)DS153 Q S P L L Q L I V G T PDS152 K T L N W L S Y A Q L ADS86 S P L S I A A S S P W PDS30 L T P H Q T T M A H F LDS150 Y H S G L H P M P P F PDS91 Q P F T T S L T P P A RDS143 M W P T T`` T H S S P Y HDS84 L I A H S M P P R T R IDS36 M I P N T W E M R L P FDS146 A T G T M K I T T H W FDS125 A I L R P Q L M P G S SDS34 G S T Q A W M S P P L ADS35 H F T F P Q Q Q P P R PDS69 T M G F T A P R F P H TDS38 Y V H N P Y H L P N P PDS123 V P H M P S T L D V K RDS91 Q P F T T S L T P P A RDS189 Q T W P P P L W F S T SDS78 M L T P R Y M A L T V NDS88 Q S F T T L T G P D N RDS144 S T P A H E P M P R C CDS80 S N F T T Q M T F Y T GDS142 A P P G N W R N Y L M PDS191 V A P R V Q N L H F G ADS200 S P Q H M F L P T N S VDS73 D N A N S S I R S Q T YDS75 E I Q P R Y P S T L T GDS193 G S T Q A W M S P P L ADS190 L L A D T T H H R P W TDS148 N V A S Y L S S V P D TDS71 A I A E T M S L F T K LDS145 D H Q R M N D A M K V LDS202 R L N P P S Q M D P P FDS147 D S P S Y K A I P G A SDS199 A M V L E G E S T V W PDS194 D A F T Q M P W V W T HDS201 M E G Q Y K S N L L F TDS198 I P V P K F D H P W R GDS127 G S T Q A W M S P P L ADS82 H I T L R M T D T E S RDS76 T L P A F G P R A H V LDS72 Y E S I R I G V A P S ````

Sapphire Binders: (40)

AAO1 S Y Q F S H HAAO2 S Q S G R L QAAO3 T P L N P G TAAO4 V P T R L D PAAO5 E L R P T V AAAO6 S P T G I T SAAO7 M L M P W T GAAO8 T L P N H T PAAO9 E T Q N R P MAAO10 P N M R A I SAAO11 R T T H Q A YAAO12 Q M S N A L VAAO13 L S N N S T NAAO14 H A P F P M LAAO15 D S K L D R IAAO16 Q Y N H S A NAAO17 S V T Q N K YAAO18 P P S P S L PAAO19 E A K P R F HAAO20 M N H I N S LAAO21 Q P Y N K L TAAO22 S P H G L H F

CN61 ESSRCRLVLGVRCN48 VVAGCWLQVIRRCN64 PEVRCERVALAECN80 QERKCVPILTMCCN41 FIGRRFCGAGRICN68 RIASCRKGEIRQCN83 VAWRRDVCCRLQCN92 TMEPRWWCNPISCN93 TMEPRWWCNPIN

Sarikaya et al., Ann. Rev. Mater. Res., 34, 2004

10µm

(b)(a)

(c)

Au

Selective binding ofGBP to Au.

SiO2

(b)

GBP binding to Au squares

(a)

Pt squares

Au squares

MHGKTQATSGTIQS differentiates between Au, Pt, and SiO2

SiO2

Xiaorong Xiong, Mustafa Gungormus , Candan Tamerler, Mehmet Sarikaya, and Babak A. Parviz,” Nanoscale Self-Assembly Mediated by Genetically Engineered Gold-Binding Polypeptide”, 5th IEEE Conference on Nanotechnology, paper # TU-PS8-3, Nagoya, Japan July 11-15, 2005

6

Control (no polypeptide on the pads)

With gold-binding polypeptide on the pads

20µm

Peptide-mediated self-assembly of micron-scale particles

Mustafa Gungormus, Xiaorong Xiong, Candan Tamerler, Babak A. Parviz, and Mehmet Sarikaya, “Using genetically engineered gold binding polypeptide for micron-scale self-assembly”, proceedings of the Foundations of Nanoscience Conference (Self-assembled architectures and devices), pp. 85-88, Snowbird, Utah April 24-28, 2005

Electronic control of the polypeptide assembly

+ 0.5 V bias

- 0.5 V bias

Xiaorong Xiong, Mustafa Gungormus, Candan Tamerler, Mehmet Sarikaya, and Babak Parviz, “Electronic Control of Binding of Genetically Engineered Polypeptides to Microfabricated Structures”, to be presented at the 19th IEEE International Conference on MicroElectroMechanicalSystems (MEMS), Istanbul, Turkey, January 22-26, 2006

1 nm

10 nm

100 nm

1 µm

10 µm

100 µm

Self-assembled molecular electronics

Engineered DNA networks as templates for nanoelectronic circuits

Using genetically engineered polypeptidesto guide self-assembly

Self-assembling Si circuits on plastic

Self-assembled silicon networks1 mm

1 cm Shape recognition for self-assembly

Putting CMOS on plastic, easily re-configurable circuits

Cheap, “device” integration, macroelectronics

300 µm 120 µm

Element could be a transistor or a LED, or …

Solder only ‘wets’ the gold on the element during assembly.

Surface Tension forces of the molten Solder help to drive the assembly.Si Substrate

Element

Molten Solder Dots

Binding Site

Shape Recognition for

part to template Self-Assembly

SU-8 forms the sidewalls.

Microfabricatedparts Template with

Complementary shapes

SA is performed with submerged parts and template

Fabrication ProcessElements

400 µm Si Handle

20 µm Si Device Layer

2 µm Oxide

1) Evaporate Au on top of Device Layer

2) Deep Reactive Ion Etch (DRIE) through Device layer to Oxide

Photoresist Mask

3) Etch Oxide in HF to release elements

Template

1) EvaporateAuon Si or PET Substrate

2) Pattern 10 µm to 20 µm thick SU-8 to form shapes

3) Dip-coat Au with low melting point alloy

100µm - 300µm

140µm - 340µm

7

Shape recognition for self-assembly Self-assembly

Sean A. Stauth, and Babak A. Parviz,” Self-assembled silicon networks on plastic”, proceedings of the 13th International Conference on Solid-State Sensors, Actuators, and Microsystems (Transducers’ 2005) ,pp. 964-967, Seoul, Korea June 5-9, 2005

Active and passive self-assembly results

Single crystal silicon Field Effect Transistors

I-V Curve through Assembled Elements

-10

0

10

-2 -1 0 1 2

Voltage Across Elements (V)

Cur

ren

t (m

A)

Self-assembly results

Assembling 10000 silicon components with 95% yield on plastic

100 µm Silicon parts

1 nm

10 nm

100 nm

1 µm

10 µm

100 µm

Self-assembled molecular electronics

Engineered DNA networks as templates for nanoelectronic circuits

Using genetically engineered polypeptidesto guide self-assembly

Self-assembling Si circuits on plastic

Self-assembled silicon networks1 mm

1 cmSelf-Assembling Silicon Networks

• Goal: to make micron-sized silicon elements that can self-assemble into an electrical network (electronic powder)

• Making a 2-D network structure that can be expandedto 3-D

• Incompatible process integration• First cut: CMOS compatible• Driving force: low Tmelt alloy• 100 micron size scale• Use available solid-state

Fabrication technologies

Towards 3-D self-assembled Si circuits

8

Fabrication Process Fabrication Process

Elements on the surfaceof the wafer

200 µm

Jianchun Dong, Babak A. Parviz, Hong Ma, Alex Jen, “Using self-assembly for the construction of nano-scale lateral transport molecular electronic devices and micro-scale silicon-based networks”, Invited paper, Proceeding of Optics East (Nanosensing: Materials and Devices), pp. 112-122, Philadelphia, October 25th – 28th 2004

Fabrication Process The Assembly Process

The Assembled Network

Elements before assembly Elements after assembly

Towards 3D silicon circuits

Programming the self-assembly process at an interface

• How to fabricate, experiment1) Photoresist pattern on SOI wafer

2) Plasma etch

3) Release parts with HF acid

140 µm

140 µm

Investigating the use of magnetic (Ni) strips on parts to aid in agitation

9

Towards 3D Self-assembly

Binding mechanism: capillaryAgitation: gravity / impact / fluidic

2. Self-assembly of macromolecule (polymer) on SAM surface

3. Self-assembly into mm-scale structures

Binding mechanism: covalent bondsAgitation: thermal

Binding mechanism: hydrophobic / hydrophilicAgitation: fluidic

10 nm

1. Self-assembly of molecules on surface.

10 µm 0.5 mm

Christopher J. Morris, Sean A. Stauth, and Babak A. Parviz, “Using Capillary Forces for Self-Assembly of Functional Microstructures”, proceedings of the Foundations of Nanoscience Conference (Self-assembled architectures and devices), pp. 52-56, Snowbird, Utah April 24-28, 2005

Hierarchical self-assembly scheme across the size-scale

Towards 3D Self-assembly

Self-assembled microparts

A and Bare soluble

Chemically-patterned surfaces

A + B B + C

A + BDecant excess A, B, C

C

A

C

a) b)

c)

Christopher J. Morris, Harvey Ho, and Babak A. Parviz, “Insoluble Liquid Energy Minimization for Polymer Deposition on Free-StandingMicrofabricated Parts”, submitted to the ASME/IEEE Journal of Microelectromechanical Systems

Self-assembly in Solution

Christopher J. Morris, Harvey Ho, and Babak A. Parviz, “Using Insolubility Wave-front for Polymer Deposition on Self-AssemblingMicrofabricated Parts”, Proceedings of The 2005 International Conference on MEMS, Nano, and Smart Systems, pp. 223-227, Banff, Alberta, Canada July 24-29, 2005

Acknowledgements• Postdoctoral Research Fellows

– Ranjana Mehta– Xiaorong Xiang (now at Intel)

• Grad Students– Jianchun Dong– Harvey Ho– Sam Kim (with D. Meldrum)– John Lund– Chris Morris– Ehsan Saeedi– Angela Shum– Sean Stauth– Jean Wang (with Lih Lin)

• Undergrad Student– Walt Wyman

Washington Technology CenterCenter for Nanotechnology at the University of WashingtonFunding for this work was provided by NIH, DARPA, NSF, and University Initiative Fund (UIF) at UW

Collaborators:Alex Jen (Mat. Sci)Mehmet Sarikaya (Mat. Sci)Mary Lidstrom (Microbiology)Lih Lin (Electrical Eng.)Chengde Mao (Chem, Purdue)Deirdre Meldrum (Electrical Eng.)

Questions?

a

b

efg

hc

d

Self-Assembly contributes

here…

Serial assembly?

Opel

HLX 8100

MEMSPI.com

Eigler (IBM)

Christopher J. Morris, Sean S. Stauth, and Babak A. Parviz, “Self-assembly for micro and nano scale packaging: steps towards self-packaging”, to appear in the November 2005 issues of IEEE Transactions on Advanced Packaging