Maruyama-Chiashi Lab. - Creating Catalyst-containing ...maruyama/visitors/Jennifer...Raman...
Transcript of Maruyama-Chiashi Lab. - Creating Catalyst-containing ...maruyama/visitors/Jennifer...Raman...
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Creating Catalyst-containing Nanostructures via Self-assembled Block Copolymer Templates for
Rationally Synthesis of 1D nanostructures
Jennifer Lu
University of California, MercedAgilent Technologies
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Carbon NanotubesExcellent mechanical properties: Composite
100 to 200 times stronger than steel
Space cable (NASA) CNT-based X ray (UNC)
CNT: 109A/cm2 Metal: < 106A/cm2 Si: < 103A/cm2
High aspect ratio, huge current capability: Field emission tips
Source Drain
GateGate Oxide
CNT
CNTFET(IBM)
Ballistic electron transport property
µ ~ 3000 to 20,000 cm2/V-sec max reported in p-type CNTFETs
µ ~ 500 cm2/V-sec Si-pFETs
Excellent electron transport property: Transistors
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Nanowires
0.9 ng/ml
1.4 pg/ml
0.2 ng/ml
0.5 ng/ml 0.5 pg/ml
0.2 pg/ml
mucin-1(Overian and Breast)
CEA(Intestinal)
PSA(Prostate)
G. Zheng, F. Patolsky, Y. Cui, W.U. Wang, C.M. Lieber, Nat. Biotechnol. , 23, 1294 (2005)
Multiplexed electrical detection of cancers
Electronic based sensor
CdS
Perform Laser surgery
NanoLaser
X. Duan, Y. Huang, R.Agarwal. C.Lieber. Nature 421, 241–245 (2003)
Nano-electricity generators
ZnO
Z.L. Wang Georgia Tech
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Challenges
Lack of controllable synthesis prevents realizing their highly touted properties
LocationsOrientationsProperties
PredictableConsistent
CommercializationNanotechnology !!! Controllable synthesis
Substrate 700Substrate 700––950 950 °°CC
Catalystnanoparticle
CnHm
CnHm CnHm
CC CC
Nucleation Growth
AlloyEutect PrecursorsMetal
catalyst
Vapor -liquid -solid (VLS) Nanowire growth Nanotubegrowth
Location and diameter are determined by catalyst
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Challenges
Controllable growth → Catalysts with controlled size and spacing at predefined locations
Transition metalCarbon nanotubes: Fe, Co, Ni
Nanowires: Au: InP, InAlAs, GaN, SiNi: GaN, SiC, Si
Current top-down lithography
≤ 3 nm for single-walled carbon nanotubes ≤ 20 nm for nanowires
Catalyst nanoparticle size
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Outline
• Background: Block copolymers
• Iron-containing nanostructures for CNT growth
Thin film self-assembled iron-containing block copolymers
• Catalytically active transition nanoparticles for CNT and Si nanowire growth
Solution self-assembled metal modified block copolymers
• Conclusion
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Outline
• Background: Block copolymers
• Iron-containing nanostructures for CNT growth
Thin film self-assembled iron-containing block copolymers
• Catalytically active transition nanoparticles for CNT and Si nanowire growth
Solution self-assembled metal modified block copolymers
• Conclusion
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Nanomorphologies Produced by Diblock Copolymer
covalent link
S. Föster et al, Adv. Mater. 10, No. 3, 1998
Morphology← Volume fraction of componentMicrodomain size← Total molecular weight
< 60 nm
A BMetal containing
Non-metal containing
Self-organize metal-containing block copolymer to produce metal-based nanostructures (A)with periodic size and spacing surrounded by (B)
Template for generating metal-containing nanostructures
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Outline
• Background: Block copolymers
• Iron-containing nanostructures for CNT growth
Thin film self-assembled iron-containing block copolymers
• Catalytically active transition nanoparticles for CNT and Si nanowire growth
Solution self-assembled metal modified block copolymers
• Conclusion
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Iron-containing Ferrocenylsilane Block CopolymersIron is a well-known catalyst system for CNT growth
PS450-b-PFEMS25 (ΦPFEMS=0.10) PS389-b-PFEMS108 (ΦPFEMS=0.36) PS539-b-PFEMS296 (ΦPFEMS=0.53)
Spherical Cylindrical Laminar
Discrete nanostructures
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Thin film Self-assembled Morphologies
25vol% 263 44
Cylindrical
33vol% 402 98
Cylindrical Cylindrical
36vol% 389 108
Size and spacing can be adjusted by chain lengths
ØPFS PS PFS Domain size Spacing
0.33
0.25
0.36
14 2844253
402 98
389 108
22 36
31 45
11vol% 542 39
Spherical
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Iron-Containing Nanostructures for CNT growthSelf-assembled polymer thin film
CNT growthOxygen plasma
Fe-containing silica posts
Carbon nanotube uniformly distributed over a large surface area!
AFM and Raman analysis:1 nm in diameter on averagevery few defects in CNTs
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Si Rich Ferrocenylsilane-based Copolymer Systems
EtEt
SiO2 may further reduce aggregation SiO2 Spacer
Oxygen plasma
PMVS377-b-PFEMS25 (13vol% PFEMS) PMVS837-b-PFEMS45 (11vol% PFEMS)
1 µm by 1 µm scan10 nm in height
AFM height image
4 µm by 4 µm
SEM image
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Tailoring CNTs by Adjusting Block Lengths
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.00
5
10
15
20
25
30
Freq
uenc
y
Tube diameter(nm)0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.00
5
10
15
20
25
30
Freq
uenc
y
Tube Diameter(nm)
Mean=1.6 nm
PMVS837-b-PFEMS45 PMVS377-b-PFEMS25
Mean=1.1 nm
Tailoring polymer chain lengths → Fe-containing nanostructure size & density → CNT diameter & density
Rationally synthesize CNTs with predictable and tunable size and density
G/D= 12 (1.6 nm) PMVS837-b-PFEMS45
PMVS377-b-PFEMS25 G/D= 6 (1.1 nm) Growth condition for producing defect-free CNTsis sensitive to catalyst size.
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CNTs for Display ApplicationDisplay Market: $50 billion per annum
• Thinner• Brighter• Better color reproduction • Faster response time• Lower power consumption
A cluster of CNTs
- - -
+ + +
Directly grow uniform upright few-walled CNTs on ITO coated glass
Few-walled CNTs
Excellent field emission properties Superior mechanical integrity
Few-walled tubes
Courtesy of Xintek
Singal-walled tubes
Multi-walled CNTs
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CNTs for Display Application
Catalyst: Fe-containing nanostructures (PS389-b-PFEMS108)Carbon nanotube growth condition: PECVD, 600ºC
Tubes are upright! 3 walls
1 µm
Excellent Field emission!
Uniformly dispersed catalyst species Uniform emission
Excellent emission propertiesTailoring block lengths
Upright few-walled CNTs
Evenly populated CNTs
PS-b-PFEMS block copolymer template:
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Selective Growth of CNTsCombination of top-down litho with bottom-up self-assembly
0.9µm islands
Self-assembly and lithography patterning processes on a 3 inch wafer format
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Diameters of CNTs Grown from Catalyst Islands
170 200 230 260 290 320 350 380
Wavenum ber(cm ^-1)
Ram
an In
tens
ity(a
.u.)
CNT(174)
Si
CNT(284)
CNT(386)
CNT(196)
632nm laser
1.3nm
0.7nm0.6nm
1.5µm by 1.5µm scan
Majority of tubes have diameters around or less than 1nm
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Conventional Transistor DesignEither directly growing CNTs or dispensing as-synthesized CNTs,
electrical contact is a random event! not manufacturable process!
“Mod3” tubes, tubes with n-m=3i(i=integer) are small gap semiconductor with Eg ~1/d2
All other tubes are moderate gap semiconductor with Eg ~1/d
Variations in Channel lengthEg (diameter, chirality)
UnpredictableInconsistent Device performance
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Circular Transistor Design
Drain
• Weighted average of many tubes• Increase current carrying capacity and gm
Greatly improve consistency and predictability
• Diameter and chiral arrangement• Orientation• Length
Alleviate requirements
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Selective Growth of Suspended CNTs
Suspended tubes are free ofinteraction with underlying substrates
Characterize CNTs by optical means
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Raman Characterization
1.2 nm
Si G-band RBM between 160 to 230cm -1
Trench Suspended tubes
Si G-band RBM between 160 to 230cm -1
Trench Suspended tubes1.2 nm
Radial breathing mode
100 150 200 250 300
Ram
an In
tens
ity(a
.u.)
In-plane carbon oscillation mode
1200 1300 1400 1500 1600 1700 1800
Raman shift (cm-1)
suspendedon surface
suspendedon surface
Radial breathing mode
100 150 200 250 300
Ram
an In
tens
ity(a
.u.)
In-plane carbon oscillation mode
1200 1300 1400 1500 1600 1700 1800
Raman shift (cm-1)
suspendedon surface
suspendedon surface
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Selective Growth of Suspended CNTs
Ultra-sensitive Mechanical SensorMechanical perturbation induces change in resistance
Nano-mechanical SwitchCNTs mechanically deflected to establish electrical contact
Nano-oscillator
Nanoelectromechnical applications
Suspended tubes are free ofinteraction with underlying substrates
Characterize CNTs by optical meansIdeal p-n junction diode (GE)Greatly enhanced IR emission (IBM)
Block copolymer → controllable synthesis suspended CNTs → facilitate device applications
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Summary: Thin film self-assembledFerrocenylsilane-based Block Copolymers
Iron-containing nanostructures with precise control in size and spacing have been generated by this block template
Uniformly distributed and high-quality CNT mats have been produced
Selective growth of CNTs on a surface or in suspension has been demonstrated
CNTs with diameters ∼1 nm
Few-walled, upright CNTs have been synthesized at 600ºC with excellent emission properties
CNT’s size and density can be adjusted by tailoring block lengths
For a given growth condition, the amount of dangling bonds varies with catalyst size.To achieve defect-free CNTs with consistent properties,
it is essential to have uniform sized catalytically active nanostructures.
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Outline
• Background: Block copolymers
• Iron-containing nanostructures for CNT growth
Thin film self-assembled iron-containing block copolymers
• Catalytically active transition nanoparticles for CNT and Si nanowire growth
Solution self-assembled metal modified block copolymers
• Conclusion
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PS-b-P2VP:Metal-induced Micellization
141CH2 CH CH2 CH
475N
PS -b-P2VP
M
M2+
M2+
M2+
M2+
M2+
M2+
Metal inducedmicellization
Surface micelles iron-complexed PS-b-P2VP
Iron nanoparticlesAFM height images1 by 1µm scan
No surface micelles !PS-b-P2VP
Toluene
FeCl2
2 nm!
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Solution Self-assembly: Various Metal Nanoparticles
FeNi Co
MoFeNiFe
AFM height images:10 nm in Z scale, 1 by 1µm scan
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CNT Mats
Inte
nsity
(A.U
)
Raman shift (cm -1 )
CoFe
2 µm
2 µm2 µm
Co/Mo=1:3Fe/Mo=1:8
2 µm
Fe/NiNi
2 µm2 µm
High quality CNTs and uniformity maintained over a large surface area
Growth mechanism: Effect of catalyst composition
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Tuning Size & Spacing
PS475-b-P2VP141
2.6nm, 45 nmPS319-b-P2VP76
1.8 nm, 39 nm
PS2128-b-P2VP539
7.5 nm, 81 nm
PS794-b-P2VP139
4.2 nm, 70 nm
PS524-b-P2VP85
3.3 nm, 49 nm
3.8 nm, 140 nm
AFM height images1 by 1µm scanSize and spacing dictated by block lengths
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Narrowing Spacing by Adjusting Solution Concentration
0.5 wt % PS475-b-P2VP141 1.0 wt % PS475-b-P2VP141
An array of closely packed cobalt nanoparticlesto promote vertically oriented CNTs can be formed!
AFM height images1 by 1µm scan
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CNT Diameter ControlAfter UV-Ozonation After thermal treatment (900°C/20min in H2)
Catalyst nanoparticles do not agglomerate at high growth temperature
Average particle size: 1.9 nm Average particle size: 1.0 nm
Phase image
AFM height images1 by 1µm scanIron nanoparticles
0.83nm0.83nm
Diameter (nm)
Num
ber o
f tub
e m
easu
red
AFM: 0.5 ~ 1.5 nmRaman: 0.7 ~ 1.3 nm
0
2
4
6
8
10
12
14
16Raman
AFM
0.5 0.7 0.9 1.1 1.3 1.5
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CNT 2D film
Nanoparticle size (nm) CNT diameter (nm)
PS475-b-P2VP141 2.2 (±0.1) 1.1(±0.4)
1.7(±0.5)PS794-b-P2VP139 3.8 (±0.2)
Inte
nsity
(A.U
)
Raman shift (cm -1 )
10 µm10 µm
PS794-b-P2VP139PS475-b-P2VP141
Electronic signal: Average properties of the individual CNTsOnly density matters!
Controlled by the block copolymer approach
Thin-film transistor (high carrier mobility)SensorMALDI-MS target
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MALDI-MSMALDI(Matrix Assisted Laser Desorption and Ionization)
is a technique for ionization of large molecules for Mass Spectroscopic detection
Biopolymer is dissolved in a solvent
Matrix molecule is added (e.g. trans-cinnamic acid, 10,000 times more than biopolymer).
UV-Laser causes the disintegration of matrix
Evaporation and ionization of biopolymers
Positively charged fragmented ions are accelerated and detected
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Carbon Nanotube Coated Surface as MALDI Target
500 attomoles BSA (bovine serum albumin) in 0.25 mg/mL CHCA matrix
899.5
927.5
974.5
1073.5
1163.7
1249.6
1305.7
1465.3
1534.5
1567.5
1639.7
1682.8
1734.4
1882.6
0
500
1000
800 1000 1200 1400 1600 1800 2000 m/z
Score: 146 ( > 66)Coverage:29%
Positive Identification
CNT- coated Surface
877.2 927.5
1050.1 1169.4 1261.11305.6
1465.4
1534.6
1567.6
1640.8
1734.4 1881.8
0
500
1000
800 1000 1200 1400 1600 1800 2000 m/z
No Identification
TiN Target
m/e m/e
Able to identify 500 attomoles of bovine serum albumin using CNT surfaces
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Catalyst Support
SiO2Si3N4Mo
Fail to reduce to 0
No CNTssparse, short , largedense, long, smallCNT
0.52% (+3)0.56% (+3)0.53% (+3)Fe Before growth
<0.1%(0)
Mo
0.21% (0)
SiO2
Fe After growth <0.1%(+2, +3)
Si3N4
Fe nanoparticles adhere poorly on Mo and Si3N4 surfaces
Growth mechanism: Effect of catalyst support
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Growth Mechanism: Carbon feed rate
Ethane 140ppm
Ethane 14400ppm
Ethane 1600ppm
1.2 nm
1.3 nm
1.8 nm
SWNT growing
Under fed
Low Carbon Feeding rate
Under fed
SWNT growing
High Carbon Feeding rate
overloaded overloaded
Collaboration with Duke
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Lithographic Selective Growth
Patterned PS-b-CoPVP
50 µm
Strip the resistApply a bilayer resist
Strip underlayer Apply catalyst BCP
Selective growth of CNTs over a large surface area!
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CNT Growth Results
0.9 nm1.0 nm
0.9 nm0.9 nm1.0 nm
0.9 nm
Catalyst rings
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Electrical Test Results
-4.0E+03
-3.0E+03
-2.0E+03
-1.0E+03
0.0E+00
1.0E+03
2.0E+03
3.0E+03
4.0E+03
-0.15 -0.1 -0.05 0 0.05 0.1 0.15
Vsd(V)
Isd(
nA)
Vg= 0
Vg= -1
Vg= -2
Vg= -3
Vg= -4
-4.0E+03
-3.0E+03
-2.0E+03
-1.0E+03
0.0E+00
1.0E+03
2.0E+03
3.0E+03
4.0E+03
-0.15 -0.1 -0.05 0 0.05 0.1 0.15
Vsd(V)
Isd(
nA)
Vg= 0
Vg= -1
Vg= -2
Vg= -3
Vg= -4
Optical lithography to define catalyst nanostructure arrays on a wafer format
Source and Drain
CNT growth
∆Vg= 4V25 kohm to 75 kohm
Decent tubesGood metal contact
Resistance is 30 kΩ at zero bias>7 µA pass through
3 inch process! However, tube density is extremely low!
Wafer level processing for fabricating CNT- based electronics
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Summary: Solution Self-assembledPS-b-PVP Micelles
Highly ordered nanoparticles with tunable composition, size and spacing on varioussurfaces can be produced
Uniformly distributed and high-quality CNT mats have been obtained
CNTs with diameters ∼ 1 nm have been synthesized using Co nanoparticles
Selective growth of CNTs on a surface or in suspension has been demonstrated
Wafer–level fabrication of CNT-based electronic devices has been established
Provide an opportunity of studying the growth mechanism Catalyst compositionCatalyst supportCarbon stock feed rate
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Silicon Nanowires from Au Nanoparticles
Au nanoparticles: 5 nm
2µm
Si nanowires
PS475-b-P2VP141HAuCl4
NHAuCl4
AuCl4N
H
AFM height images1 by 1µm scan, 10 nm in height
80859095100
Binding energy (ev)
Inte
nsity
(a.u
)
Au(0)Au47f/2
Wafer-level growth
(20~80 nm from catalyst breaking up 1 nm Au thin film)
7~9 nm in diameter
20 nm
~ 7.5 nm
6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.00
1
2
3
4
5
6
7
Freq
uenc
y
Diameter (nm)
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Outline
• Background: Block copolymers
• Iron-containing nanostructures for CNT growth
Thin film self-assembled iron-containing block copolymers
• Catalytically active transition nanoparticles for CNT and Si nanowire growth
Solution self-assembled metal modified block copolymers
• Conclusion
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Important Attribute of Block Copolymer Template
NanoSize and Spacing: Mw of each segment
Number of metal atoms incorporated onto a polymer chain
Micro and sub-microLithography
MacroSuperior film forming capability
serves as a carrier to uniformly distribute nanostructures across a wafer
Ability to control at nano-, micro- and macro-scales simultaneously
Controllable synthesis of 1D nanostructures on a wafer format
Fully compatible with existing semiconductor processes
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Conclusion
Thin film self-assemblyFerrocenylsilane-based diblock copolymer
Solution self-assembly Various metal-complexed PS-b-PVP
Metal-containing nanostructures with controllable and tunable
size, spacing and composition
CNTs and Si nanowires: uniform density, narrow diameter distribution, spatially controlled
Predictable and reproducible nanofabrication method
Applications: Transistor, Display, MALDI-MS targets, NEMS
Understanding growth mechanism:Catalyst sizeCatalyst supportCarbon stock feeding rate
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Current Collaborators
University of Toronto
Prof. Mitch Winnik
David Rider
Duke University
Prof. Jie Liu
Chen Qian
Bristol University
Prof. Ian Manners
MIT
Prof. Mildred Dresselhaus
Hyungbin Son
University of North Carolina at Chapel Hill
Prof. Otto Zhou
Eric Peng
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Thanks you!