Will enable use of BCP templating in low cost applications (roll to roll, extrusion).
• Surfactants as proxy for compositionally heterogeneous materials. We find ...
Cluster R Roll-to-Roll Processing of Nanostructured Materials and Devices
Our Objectives • Create Low Cost Nanotechnology-Enabled Devices • Merge Self-Assembly with Traditional Web-Based Processing - compatibility with flex electronics, advanced printing and converting • Develop Versatile R2R Nanoimprint Lithography Platform - device patterning, substrate texturing, function device layers - emphasis on new materials and capabilities
• Develop and Demonstrate Tool Platforms in a Test Bed Facility • Leverage CHM Investments in Basic Science - the CHM is a $4M/yr NSF Nanoscale Science and Engineering Center • Develop Commercializable Outcomes with Industry - CHM technical staff to assist
Low Cost Nanodevices by Combining Printed Electronics and Nanostructured Device Layers • Start with Printed Macroelectronic Substrate - low cost, low performance - simple devices - micron ++ length scales
printedelectronicsnews.com
• Add Nanostructured Device Layers via Low Cost Processing - low cost, large area - length scales less than 50 nm, polymer / NP hybrids - simple as coat-able dielectrics, TCOs, barriers - enabled or enhanced functionality due to ordered nanostructure - device patterning by nanoimprint lithography - PVs, energy storage, magnetic metamaterials, sensors, supercaps • Produce Low Cost, High Performance Nanotech-enabled Devices Signal Processing - single purpose first Solar PV Communications Interface Energy Harvesting - PV, battery, sensor, antenna Nanoparticle Metamaterial Nanoparticle Sensor Antenna/RFID - integrated devices
Li+ Energy Storage
Macroelectronic Flex Substrate
Top Down Meets Bottom Up ….. on a Web
Challenges for R2R Manufacturing of Nanostructured Materials and Devices • Materials and Process Costs • Planarization and Base / Barrier Layers - includes transparent conducting films, coat-able dielectrics • Creation of Ordered Nanoscale Hybrid Materials as Active Layers - directed and/or additive driven self-assembly • Continuous Device Level Patterning (Ken Carter) - roll-to-roll nanoimprint lithography • Availability of Collaborative Demonstration Facilities / POC Projects - UMass CHM R2R Tool Platforms - PVs, flexible memory as example devices
Nanotechnology Is Enabling but Many Important Applications are Cost Sensitive Energy, Water, and Flexible Electronics Nanomanufacturing Must Adapt to Serve Low Cost Per Area Devices Spheres
Cylinders
Lamellae
Cylinders
Spheres
Li+
• Morphology is key to performance • BCP template yields periodic structures (5 – 45 nm domains) • Hybrid materials for functionality - co-assembly required • Roll-to-Roll manufacturing • Integration with top down processes
Target ~ $25/m2
Controlling Morphology at the Nanoscale Can Be Critical to Device Performance
Modify Properties with NPs
High Magnetic Permeability Metamaterials
HfO2
NPs =
Miniature, low loss, high band width antennas
Synthesis of NPs with Controlled Surface Functionality
FePt CeO2
Coat Polymer/NP Hybrid Films Containing 80 wt% NPs
Block Copolymer Templates: Spontaneous Assembly upon Spin Coating, Complete Control of Morphology
Di-block Copolymer
Spheres
Cylinders
Lamellae
Cylinders
BCP Phase Diagram
Spheres
Increasing f
Key Parameters:
(Adapted from Bates, 1994; Matsen, 1996)
block volume fraction, f controls morphology Flory Parameter, N controls segregation degree of polymerization, N controls domain size
Small N requires large for strong segregation
Strengthening Phase Segregation via Segment Specific Interactions: Well-Ordered Materials by The Barrel F108 / PAA Blends 6
o
I (a. u.)
10 5 10 10
4
10
3
10
2
F108
F108 10% PAA
1
1
10 0 10 10 10
-2
F108 20% PAA
√3
1
-1
T=80 C
√7 F108 30% PAA
√2 √3
√4
√5 √7 F108 40% PAA
PAA = 8.5 kg/mol
0.0
0.5
1.0 q (1/nm)
1.5
We find blending with homopolymers that H+ bond to the majority PEO block yields exceptionally well-ordered materials by increasing segregation • Demonstrates the role of strong selective interactions in polymer assembly • Induce order in compositionally heterogeneous systems with small • Will enable use of BCP templating in low cost applications (roll to roll, extrusion) • Surfactants as proxy for compositionally heterogeneous materials
2.0
Nanoparticle Driven Assembly of Well Ordered Hybrid Materials: Disorder to Order Transitions in PEO-PPO-PEO Triblock Copolymers Induced by Functionalized Si, Au Nanoparticles or Fullerenes
3
1
Neat F108
1 neat F127
1/2
1
3
1/2
7
1
10
1/2
2
30% Si-R-NH2
I(a.u.)
I (a. u.)
10
1 2
20% C60(COOH)6
1/2
3
2
1/2
7
-1
40% Si-R-NH2
3 30% C60(COOH)6
10
0.0
0.0
0.5
1.0 -1 q (nm )
1.5
0.4
0.8
1.2
1.6
q(1/nm) OH HO
OH
• Disorder Cylinders Spheres
S S HO
S
• First demonstration of nanoparticle induced order! - addition of NPs drives system order • Robust, rapid, precision assembly of hybrid materials • Low molar mass ligands, high NP content
S
Au
S
S
OH
S S OH
HO OH
Assembly Using Fullerene Derivatives HO O
O OH
C60(COOH)2 1E7
100
1
neat F127
20% C60(COOH)2
15% Bis-PCBM
2
I(a.u.)
I (a.u.)
I (a.u.)
neat F127
1
1 1
30% C60(COOH)2
0.1
20% C60(COOH)6
2
3 30% C60(COOH)6
1/2
3
40% C60(COOH)6
1/2
30% Bis-PCBM
3
40% C60(COOH)2
0.01 0.0
neat F127
1
10
1/2
7
50% C60(COOH)6
0.4
0.8
1.2
q (1/nm)
1.6
0.0
0.4
0.8
q(1/nm)
1.2
1.6
1E-3
0.0
0.4
0.8
1.2 1.6 q(1/nm)
H-bonding exists between PEO and C60-COOH Higher functionality, more favorable interaction, more order
2.0
2.4
2.8
The importance of morphology control in BHJ PV cells P3HT/PCBM 150C annealing for 1h
Transparent Electrode (ITO, ZnO)
Donor
h+
e‐
External Load
Acceptor
Metal Electrode (Al, Mg, Au)
P3HT+ PCBM Advantages: (1) Large interfacial area (2) Effective charge generation (3) Extremely fast electron transfer
Bertho, S. Sol. Energy Mater. Sol. Cells 2008, 92, 753.
Drawbacks: (1) Poorly controlled D/A domain size distribution (strongly dependent on processing conditions) (2) Morphological instability & aging (aggregation of fullerene nanocrystal)
An Example of a Device Based on Additive Driven Assembly: Block Copolythiophenes/Fullerene Blends for Photovoltaics O O Transparent Electrode
O O S S
S m
S
n
O O
Metal Electrode
O O
GISAXS – Ordered Structure
PCE VS. Processing Conditions
intensity (a.u.)
BCP BCP/PCBA=8/2 BCP/PCBA=6/4
1000
38.5nm 31.8nm 26.8nm
100
-0.4
-0.2
0.0
-1
q(nm )
0.2
0.4
VOC (V)
FF(%)
JSC (mA/cm2)
PCE (%)
as spun
0.57
53.58
6.23
1.90
pre-annealing 150C 10min
0.60
54.27
6.29
2.04
post-annealing 150C 10min
0.59
52.46
6.37
1.97
Suppression of C60 Crystallization over Extended Annealing (or Suppression of “Nanoparticle Mobility”)
5μm P3HT/bis-PCBA(6/4)
5μm
200nm
BCP/bis-PCBM(6/4)
BCP/bis-PCBA(6/4) HO O
O OH
Bis-PCBA
Annealing at 150OC for 12hr
Floating Gate Memory via Self Assembly
*
S S
*
P3HT
n
SiO2 Glass or PEN
Block-copolymer with Au NPs
Patterning of Flexible Floating Gate Memory – R2R UV-Assited NIL
plasma
etching
etching
Patterning limits will determine device density
UMass / CHM R2R NIL Tool • K.R. Carter and J. Rothstein are CHM Test Bed Coordinators • UMass NANOemBOSS R2RNIL Tool has been designed and constructed with Carpe Diem Technologies (Franklin, MA) • Tool is uniquely designed for coating and imprinting with nanoscopic precision
R2R Processing of Single Domain Block Copolymer Thin Film MiniLabo Microgravure Coater
PS-b-P2VP (55k-b-25k) on Teonex PEN 125 um Planerized Film : Phase Image
R2R Processing of Single Domain Block Copolymer Thin Film PS-b-P2VP (55k-b-25k) on Silicon. Solvent Annealed with (50:50) Toluene:Hexane 16 hrs.
Surface roughness of the Si substrate: ≤ 1 nm
2% PS-b-P2VP (55k-b-25k) in PGME solution, coated on 125 µm PET Film using the MiniLabo Microgravure Coater: 0.5m/min line speed.
Surface roughness of the PET substrate: 4.3-5.6 nm
Substrates: Planarized = $$ Polymer
Commercial Name
Thickness (micron)
PET
Melinex ST 505 (DuPont)
125
PET
Cosmoshine A4100 (Toyobo)
50
PEN Planarised
Teonex Planarised (DuPont)
125
Surface Tension (dyne/cm) 38-40
38-40
Surface Treatment
2 sides, crosslinked acrylic
Price at 125 micron $/ m2 3
2 sides, for ink adhesion
3
One side planarised, one side adhesion coating
62
Solution: In-line planarization Requirements • Polymers that dissolve in common solvents • Can be R2R coated to form good films • Can be crosslinked by heating to moderate temperatures (or by UV) • Tune composition to control surface energy • Future: form hybrid films for functionality: conductivity, high k, barrier, heat resistance AIBN
Hydrophilic + Hydrophobic Monomer Monomer
Polymerize
Random copolymer
Planarization film
Crosslink condition
Polymer 1
UV exposure 1 min/ no baking
Polymer 2
120°C, 15min
Polymer 3
120°C, 15min
Coating Results on Planarized PET Films
μ
μ
R2R coating of 3% PS-b-PtBA on PET Melinex ST505 substrate using planarization layer applied by microgravure
Roll-to-Roll Coating of Ordered Hybrids • • • •
Two interchangeable gravure or Mayer rod coaters placed in series First coater used to apply a planarization layer Second coater used to apply thin block copolymer or hybrid layer on planarized film. Three independently controlled ovens (with room for expansion to six) used to apply temperature and environmental gradient along web. Zone 1
First Coater for Inline Planarization of Film
Zone 2
Second Coater to Deposit Block Copolymer Film
Zone 3
Unwind with Option to Add Protection Film
Roll-to-Roll Coating of Ordered Hybrids
• • • •
Two interchangeable gravure or Mayer rod coaters placed in series First coater used to apply a planarization layer Second coater used to apply thin block copolymer or hybrid layer on planarized film. Three independently controlled ovens (with room for expansion to six) used to apply temperature and environmental gradient along web.
Progress as of 9/30
Bulk Scale Availability of NPs for Applications Hydrothermal Routes to Capped Nanoparticles: Many Examples from Tohoku (Adschiri) and ICMCB (Aymonier)
CoAl2O4
CeO2
HOOC
Fe3O4 HOOC
HOOC O O
COOH OO O O
O O HOOC
O O
O O O
COOH
O O O
OO
HOOC
COOH COOH
Recent commercialization of CeO2 and LiFePO4 (100 kg/hr) in Korea (Lee, SNU, Hanwa)
Continuous Counter‐Current Hydrothermal Synthesis at Counter‐current reactor UMass Preheated fluid 400 °C
Reactor 300 °C
3/8” SS
Cooler T2 = 20 °C
Filter 0.5 µm
Precursor solution
Precursor solution 20 °C
BPR Preheater
5‐10 ml/min
Short reaction time (≤10 s) High throughput (> 1 g nanopowder per hour) Wide range of materials (oxides, metals) Tunable particle size and morphology tunable with temperature, nature of precursor, solvent and functionalizing agent
T1 Reactor
10‐20 ml/min
Outlet
T1 = 270 °C
Cooler Solvent (H2O, EtOH)
1/8” SS
Preheater 400 °C
Pump 1 Pump 2 Cooler BPR
T2
CeO2 NP Synthesis at UMass Oleic Acid Functionalized NPs
Bare NPs (-OH on Surface) Counts/s Ce1_step0.02_20s 60
40
20
30
50 nm
40
50
60
70
80
Hydrophilic R = COOH , NH2 or OH Hexanedioic acid (HDA) 6‐aminohexanoic acid (6‐AHA) 11‐aminoundecanoic acid (11‐AUA) 12‐aminododecanoic acid (12‐ADDA) 3‐3,4 dihydroxyphenylpropionic acid (DHPPA)
Ligands HDA 6-AHA
Aromatics
R = benzene ring(s)
Benzoic acid (BA) Biphenyl‐4‐carboxylic acid (BPCA) Naphthoic acid (NA) 3‐phenylpropionic acid (3‐PPA) 4‐phenylbutyric acid (4‐PBA) 5‐phenylvaleric acid (5‐PVA)
Short ligands Cheap (0.05-5 $/g) Stable over 250 °C Soluble in H2O or etOH
Challenges for R2R Manufacturing of Nanostructured Materials and Devices • Materials and Process Costs • Planarization and Base / Barrier Layers - includes transparent conducting films, coat-able dielectrics • Creation of Ordered Nanoscale Hybrid Materials as Active Layers - directed and/or additive driven self-assembly • Continuous Device Level Patterning - roll-to-roll nanoimprint lithography • Availability of Collaborative Demonstration Facilities / POC Projects - UMass CHM R2R Tool Platforms - PVs, flexible memory as example devices some more difficult than others, but no obvious show stoppers
31
