an overview of soft-lithographies for materials patterning...
TRANSCRIPT
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An Overview of Soft-Lithographies for Materials Patterning and Device
Fabrication
Will Childs, Keon Lee, Svetlana Mitrovski, Lindsay Elliott, John Rogers, and Ralph Nuzzo
University of Illinois at Urbana-ChampaignFrederick Seitz Materials Research Laboratory
Department of ChemistryDepartment of Materials Science and Engineering
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http://www-306.ibm.com/chips/gallery/www.just2good.co.uk/ cpuSilicon.htm
The “Si Standard” for Materials Patterning: Photolithography
WaferWith Photoresist
Pattern Copied
Lens
Photomask
Light
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p M O S n a n o - t r a n s i s t o rp M O S n a n o - t r a n s i s t o r
Intel: 30 nm
Nanoelectronics: Materials and Manufacturing Challenges
Bell past and future(?)
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Photolithography: It always wins!
Immersion Lithography: 65 nm using 193 nm ArF(limit ~35 nm)
{Resolution ~ (Wavelength/NA); NA = n x sinθ}
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Photoresists: As Good as Organic Chemistry Gets!There are so many choices (some of my favorites).
Amplified Resists SU-8: the Monster of MEMS(many variants)
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Nanofabrication: Molecular Imprints
Step and Flash
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Soft Lithography: Materials Patterning via Physical Contact/Mass Transfer
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-[Si(CH3)2-O]-n
The Core Material of Soft Lithography
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Near Field Phase-shift Photolithography
Rogers, J. A.; Paul, K. E.; Jackman, R. J., Whitesides, G. M. Appl. Phys. Lett. 1997, 70, 2658.
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head group
carbon chainsulfur
2-3
nm
The “Au Standard” for Materials Assembly: Self-Assembled Monolayers (SAMs)
1 cm
Image of Gold Surface Patterned withHydrophobic and Hydrophilic SAMs
XX X
X
xx
xx
SSS
SS
S
S
S
STM Image of a SAM
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1 cm
Image of Gold Surface Patterned withHydrophobic and Hydrophilic SAMs
1 cm1 cm
Image of Gold Surface Patterned withHydrophobic and Hydrophilic SAMs
Self-Assembled Monolayers (SAMs): Organic Materials Surface Chemistry
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Self-Assembling Monolayers (SAMs)
Laibinis, Paul E.; Whitesides,G. M.; et al. J. Am. Chem. Soc. 1991, 113, 152.
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Self-Assembled Monolayers (SAMs): an Ink
Xia, Y.; Whitesides, G. M. Angew. Chem., Int. Ed. 1998, 37, 550. Michel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697.
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Soft Lithography: Masters
Patterning TechniquesE-Beam FIB (Focused Ion Beam)
Photolithography Micromachining
Holography SPM lithography
Master
Cast/MoldPDMS
Stamp
Pattern
Transparent
Low Thermal Expansion
Chemically Inert
Reusable for patterning
Best Resolution: 2-10 nm
Poly(dimethylsiloxane)
Environmentally Safe
Silanized
Rapid Prototyping
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Microcontact Printing
a-c: Silver; e: Gold; f: copper
a+b: rolling stamp
g+h: metal as etch mask for silicon
Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Microcontact Printing: Patterned SAMs are Used to Define Fabrication Level in Au via Wet Etching
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Rogers, J. A. et. al. Proc. Nat. Acad. Sci. USA 2001, 98, 4835-4840.
Dodabalapur, A.et.al. Appl. Phys. Lett. 1998, 73, 142-144.
Electronic Paper
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20µm
spherical curvature
PZT Fresnel Lens Patterned using Microcontact Printing, a Soft-Lithographic Patterning Method
PDMS Stamp
Patterned OTS SAM on Quartz: Lift-off Patterning on Si and Glass
• Sol-gel Ceramics•Evaporated Metals
(poor as an etch resist)
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Microcontact Printing
a: polyurethane (PU)b: CuSO4c: Cu CVD on Sid: LiNbO3 CVDon Si/SiO2
Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
≤ 50 nm Resolutionof Etched Gold
Michel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697.
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MicroMolding in Capillaries (MiMIC)
a: PU on Sib: polyanilinec: ZrO2
d; polystryene colloidse+f: free standing PU
Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Jeon, N. L.; Hu, J.; Whitesides, G.M.; Erhardt, M.K.; Nuzzo, R.G. Adv. Mater. 1998, 10, 1466.
200 µm
Challenges: Registration, Resists
Ex: MOSFETs
Vd
-16 -14 -12 -10 -8 -6 -4 -2 0
Id
-0.0008
-0.0007
-0.0006
-0.0005
-0.0004
-0.0003
-0.0002
-0.0001
Vg= -4 VoltsVg= -5 VoltsVg= -6 VoltsVg= -7 Volts
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Solvent Assisted MicroMolding (SAMiM)
photoresist ona: SiO2b: polystrenec: ABS
Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Duffy, D. C.; Jackman, R. J., et al. Adv. Mater. 1999, 11, 546.
Continuous MembranePattern
Add or Remove Layer
Dry Lift-Off
Spin-Cast PDMS Membrane
Jackman, et al.; Langmuir 1999, 15, 2973.
Elastic Membrane Patterning
electroluminescent materials
plasma etch resist
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Replica Molding (ReM)
PDMS master
PU mold
Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Cohesive Transfer Lithography
PDMS molding
UVO treatment
Heat or UV curing (Closed)
Physical removal (Open)
• UVO bonded PDMS features can be torn from stamp• Works best for small feature sizes ( < 5 µm)• PDMS resists transferred from a non-composite stamp are thin ( < 100 nM)• Effective RIE/Liftoff resists—aSi, metals, etc.• Limit: composite stamps embedding a release level are exceptionally hard to master for feature sizes below 1 µm—segments detach from transfer pad during molding process.
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MicroTransfer Molding (µTM)
a+b: PU c+d: epoxy e+f: solgelXia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Quake, S.R., et al. Science 2002, 298, 580.
Integrated Microfludics
Integrated Microfluidcs
Loading Separation
Mixing Purging
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BR
AW
BWAR
High Voltage A
High Voltage B
1. 100 W Hg Arc Lamp2. Aperture Stop3. Field Stop4. Dichroic Cube Assembly5. PDMS Device6. 80:20 Beam Splitter7. Tube Camera8. R-376 PMT
S-20
(R-3
76)
Olympus AX-70
1
23
4
5
67
8
Fabrication and Detection using PDMS
place desired pattern onphotoresist & irradiatewith UV light (365nm)
spin coat STR 1075photoresist on Si wafer
wash off exposed resistwith basic developer
cure PDMS elastomer onSi/photoresist master
peel off PDMS
seal with second PDMSplanar substrate
Typical dimensions from channel intersection to reservoir are (BR) 8 mm, (AR) 8 mm, (AW) 8 mm, (BW) 60 mm. Channel cross sections ~15 µm (height) x 90 µm (width).
Schematic representation of experimental setup
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30 40 50 60 70 80 90 100 110 120
-3.8
-3.6
-3.4
-3.2
Migration Time (sec)
PMT
Sign
al (A
.U.)
0.0008 0.0006 0.0004
Mobility (cm2 / V sec)
S G F
System peak
Sugar Separation in PDMS Device at pH = 12.3
System peak
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30 40 50 60 70 80 90 100 110 120
pH = 12.6
pH = 12.3
pH = 12.0
pH = 11.5
PMT
Sign
al (A
.U.)
Migration Time (sec)
0.0008 0.0006 0.0004
Mobility (cm2 / V sec)
S G F
G
S/G/F
S/G/F
SPS F
Effect of pH on Carbohydrate Separations
SP
SP
SP
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Self Referencing Chip Design-EOF Instability
• Capillary Electrophoresis Microchips– From J. Monahan thesis:
• High pH stability• Electroosmotic flow in native PDMS
channels• Retention times have poor
reproducibility• Dye/EOF marker partitioning
• Design chip geometry to account for drift due to changes in EOF, PDMS surface, pH, temp.
• Split analyte plug down two paths of differing lengths
• Recombine for detectionBuffer Waste
Analyte ReservoirAnalyte Waste
Buffer reservoir
Pat
h 1
Pat
h 2
Detection Area
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100 150 200 250 300 350
1.0 V
Time /sec
PM
T S
igna
l /V
FITC1 FITC2
FL1 FL2
-50 0 50 100 150 200Adj. Time /sec
(a) (b)
Drifting Migration Times in Split Channel
Aligned to 1st peakFL-FITC separations
4 sequential runs
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Split Channel for CE Standardization
• Split analyte plug down two paths of differing lengths
• Recombine for detection
Buffer Waste
Analyte ReservoirAnalyte Waste
Buffer reservoir
Path
1
Path
2
Detection Area
Standardizationj
obsy
obsystd
obsxj
obsx
obsxjx )()()()( 12112
"' µµµµµµ −−+−=FITC2
jobsx
obsxstd
obszj
obsz
obszjz )()()()( 12112
"' µµµµµµ −−+−=FA2
jobsx
obsxstd
obsyj
obsy
obsyjy )()()()( 12112
"' µµµµµµ −−+−=FL2
jobsy
obsystd
obsxj
obsx
obsxjx )()()()( 12112
"' µµµµµµ −−+−=FITC2 jobsy
obsystd
obsxj
obsx
obsxjx )()()()( 12112
"' µµµµµµ −−+−=FITC2
jobsx
obsxstd
obszj
obsz
obszjz )()()()( 12112
"' µµµµµµ −−+−=FA2 jobsx
obsxstd
obszj
obsz
obszjz )()()()( 12112
"' µµµµµµ −−+−=FA2
jobsx
obsxstd
obsyj
obsy
obsyjy )()()()( 12112
"' µµµµµµ −−+−=FL2 jobsx
obsxstd
obsyj
obsy
obsyjy )()()()( 12112
"' µµµµµµ −−+−=FL2
Adjusted µa
Observed µa2 Path 2
Set µa1 of Path 1 as reference
Standardize µa1of all devices
Compensate for EOF
within runs
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FITC1 FL1 FA1 FITC2 FL2 FA2 FA2Average 96.2 105.7 135.4 179.7 197.4 254.2
Migration Time STD DEV 13.8 15.6 21.9 26.7 30.2 42.4%RSD 14.4 14.8 16.1 14.9 15.3 16.7Average 2.64E-04 2.41E-04 1.88E-04 2.05E-04 1.87E-04 1.46E-04
Mobility STD DEV 1.4E-05 1.4E-05 1.4E-05 1.1E-05 1.2E-05 1.1E-05%RSD 5.3 5.8 7.4 5.7 6.4 7.5Average 2.69E-04 2.56E-04 2.14E-04 2.09E-04
Adjusted Mobility STD DEV 9.8E-07 9.8E-07 2.4E-06 1.8E-06%RSD 0.4 0.5 1.1 0.9
( )j
eofy )12( −∆µ ( )
j
eofy )12( −∆µ( )
j
eofx )12( −∆µ ( )
j
eofx )12( −∆µ
50 100 150 200
Time /sec
PMT
Sign
al /a
.u.
0.4 V
FITC1
FITC2
FL2
FA2
FA1
FL1
Summary data for 15 separations
3 component separations
FL=fluoresceinFITC=fluorescein-isothiocyanateFA=fluorescein-amine
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Monolithic Valves and Pumps
• Multilayer structures are constructed by binding layers of PDMS
• Useful for fluidic manipulation for lab-on-a-chip
Unger, M., et.al., Science 2000, 288, 113.
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3D Microfluidics
Patterns of Cells and Proteins
Whitesides, G. M., et al., Proc. Nat. Acad. Sci. USA 2000, 97, 2409.
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Laminar
Takayama, S., et al. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 5545.
Laminar Flow Patterning
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Depletion Gradients
Fosser, K. A.; Nuzzo, R. G. Anal. Chem. 2003, 75, 5779.
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Charge Patterning
Whitesides, G. M. MRS Bull. 2002, 27, 56-65.
Exposed Area
Exposed Area
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Catalytic Patterning
Michel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697.
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Catalytic Amplification
Harada, Y.; Girolami, G. S.; Nuzzo, R. G. Langmuir 2003, 19, 5114.
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Phase-Shift Lithography
Schmid, H., et al. J. Vac. Sci. Technol. B. 1998, 16, 3422. Michel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697-717.
patterned gold lines
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Microlens Patterning
Wu, M.; Whitesides, G. M.; J. Micromech. Microeng. 2002, 12, 747-758.
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NanoTransfer Printing (nTP)
Zaumseil, J., et al. Nano Lett. 2003, 3, 1223.
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Decal Transfer Lithography
Master and PDMS
UVO TreatmentOf PDMS
Heat or UV exposure
Adhesive PatternTransfer
10 µm
2 µm
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Layer-By-Layer Printing (LBL)
Park, J.; Hammond, P. T. Adv. Mater. 2004, 16, 520.
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Rogers et al., Proc. Nat. Acad. Sci. USA 2001, 98, 4837.
Flexible and Non-Planar Substrates
Whitesides, G. M., et al. Adv. Mater. 1999, 11, 7.
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Problem and Solution?
d≥20h(h/l) range is 2.0-0.2
d (.2-20 µm); h (.5-200 µm); l (0.5-200 µm)
Sylgard 184
h-PDMSMichel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697. Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci 1998, 28, 153.
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Improved Materials
Odom, T. W., et al. Langmuir 2002, 18, 5314.
Lat
eral
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Hybrid Stamps
Michel, B.; Bernard, A., et al. IBM J. Res. & Dev. 2001, 45, 697.
2 layer stamp w/ glass backing
trilayer 2 layer w/ polymer backing
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Fabrication of High Performance Ceramic Microgear
• Free-standing mm-sized gear of borosilicon carbonitride (SiBNC)
• Can withstand harsh thermal and oxidative environments
Yang, H., et.al., Adv. Mater. 2001, 13, 54.
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Metal-oxide-semiconductor field effect transistor (MOSFET)
Jeon, H., et.al., Adv. Mater. 1998, 10, 1466.
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Half-Wave Rectifier
Deng, T., et.al., Sens. and Act. 1999, 75, 60.
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Magnetic Microfiltration
• Magnetic filtration allows for removal of paramagnetic and ferri(o)magneticparticles from diamagnetic fluids
• Arrays of micron-scale nickel posts were fabricated by soft lithography and electrodepostion
• Magnetic filters integrated into microfluidic systems reduces the size of the system
Deng, T., et.al., Appl. Phys. Lett., 2002,80, 461.
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Light-emitting Diodes
• Soft contact lamination provides a means for establishing electrical contacts at room temperature in ambient conditions
• Applications: – Conformable light sources – Nanoscale optoelectronics
Lee, T., et.al.,PNAS 2004, 101, 429.
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Patterning Spherical Surfaces
• Uses in optical and sensing devices with wide fields of view (>60º)
• Limits of lithography– Depth of focus limits
topography to ±λ/2– Planar mask only comes
into contact a single point – only a small area will be in
focus
Paul, K., et.al., Adv. Funct. Mater. 2003, 13(4), 259.
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Thin-Film Transistors
• TFTs are used to address pixels in flat panel displays
• Eye focuses images on a spherically curved retina
Erhardt, M., et.al.,Chem. Mater. 2000, 12, 3306.
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Microcontact Printing DNA
S.A. Lange, V. Benes, D.P. Kern, J.K.H. Horber, A. Bernard, Anal. Chem. 2004, 76, 1641.
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Microcontact Printing Proteins
H. Wolf et al. IBM Journal of Research & Development. 2001, 45, 697.
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Affinity Contact Printing of Proteins
J.P. Renault, A. Bernard, D. Juncker, B. Michel, H.R. Bosshard, E. Delamarche, Angew. Chem. Int.Ed. 2002, 41, 2320.
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Separation of Biomolecules
Tryptic digest of FITC-BSA
S. Sia, G.M. Whitesides, Electrophoresis. 2003, 24, 3563.
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Immunoassays
A. Bernard, B. Michel, E. Delamarche, Anal. Chem. 2001, 73, 8.