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Drop Casting Method
Drop Casting Method
Drop Casting Method
Maddalena Binda
Organic Electronics: principles, devices and applications
Milano, November 15-18th, 2011
Overview
DEPOSITION PATTERNING
Drop casting Screen printing
Spin coating Soft Lithography
Doctor Blade NIL/Embossing
Dip coating Physical Delamination
Layer-by-layer, Photopatterning
Organic Langmuir-Blodgett Ink-jet printing
materials Spray coating
M. Caironi
1
Solution processable materials:
deposition techniques
Drop casting
Spin coating
Dip coating
Layer-by-layer:
Langmuir-Blodgett
Spray coating
Drop Casting
Dropping of solution and spontaneous solvent evaporation
Evaporation
Dropping
Tricks...
Combination of solvents
Solvents evaporation time: heating of the substrate to speed up the
evaporation process and/or improve film morphology
2
Spin Coating I
Dropping on spinning substrate
Film thickness:
substrate
dependent on many controllable parameters
d/dt, , t, solution viscosity,
Tricks...
McCulloch et Al., 180C
Thermal annealing
Nat. Mater., 5, 328, (2006)
(post-deposition)
Spin Coating II
Film thickness:
1/ 2
2v 1 4 = fluid viscosity = rotation speed
2 r h(t ) t
z 2 3 = fluid density v = radial velocity
3
Spin Coating III
Film thickness:
evaporation
flow dominated dominated
4
Doctor Blading I
Spreading through a moving blade onto a stationary substrate
stationary moving
Doctor Blading II
Film thickness:
5
Doctor Blading refinement I:
zone casting
Controlled orientation of deposited layers
Diluited solution
Pre-heated substrates
Top wafer lyophobic
6
Dip Coating
The substrate is dipped into the solution and then withdrawn at a
controlled speed.
Film thickness:
Thickness (H) determined by the balance
of forces at the liquid-substrate interface
Landau and Levich equation:
0.94 v 2 / 3
H
1 / 6 g 1 / 2
= fluid viscosity v = withdrawal speed
Solution = fluid density g = gravitational acceleration
= surface tension (liquid-air)
Hydrophilic head
Hydrophobic tail
Molecules move as in a bi-dimensional
ideal gas, with a well defined surface
pressure P, area A, and density
Amphiphilic molecules
3D Gas 2D Gas
water P [N/m2] P [N/m]
V [m3] A [m2]
N [m-3] n [m-2]
T [k] T [k]
7
Extreme thickness control:
Langmuir-Blodgett film II
Isothermal curve
P [Nm-1]
solid Reducing the available area, pressure
increases and eventually a phase-change
occurs: gas liquid solid
Pc l/s
Once PC is reached, a compact molecular
mono-layer is formed (solid state) and
liquid
floats on the water surface. At this stage
the area cannot be further reduced
g/l without destroying the mono-layer.
gas
A [m2]
Feedback
8
Extreme thickness control:
Langmuir-Blodgett film IV
Excellent control of thickness. X Only amphyphilic molecules can
An ideal monolayer can be grown be deposited
Homogeneity over large areas X Non trivial setup
Multilayer structures with varying
layer composition
Spray Coating
Substrate is hit by a vaporized solution flux
Nozzle trajectory
The film morphology can be controlled by:
o air pressure
o solution viscosity
o solvent properties (evaporation rate,)
o gun tip geometry
substrate o distance between nozzle and substrate
single pass technique: multiple pass technique:
droplets merge on the substrate droplets dry independently
into a full wet film before drying
smooth films rough film, but wettability issues
can be overcome
9
Spray Coating
Example 1. Girotto et al. Adv. Funct. Mater. 2011, 21, 6472
Spray-coated organic solar cells
Example 2.
Organic light sensor directly deposited onto a Plastic Optical Fiber (POF)
100n 1mW
10W
Current [A]
Spray coated 10n
LIGHT
bottom electrode 1W
1n
DARK
100p
0 10 20 30 40 50
Time [s]
Compression molding
Solid state processing from powders
10
Compression molding
Radial molecular flow during compression molding
11
Screen Printing
The solution of the active material is squeezed
through a screen mask onto the substrate surface
It can be applied to spray coating and doctor blading
Substrate
Mask
12
Shadow masking+selective wettability
Journal of Polymer Science B: Polymer Physics, 49, 15901596, 2011
Soft Lithography
Earliest motivation: overcome cost of photolithography for sub 100nm features
Basic idea: replicate patterns generated by photolithography through an
elastomeric mold.
Master
Photolithography
X-Ray Litho
EB Litho
FIB writing
Elastomer
13
Micro-Contact Printing (CP) I
Stamping of an ink through the elastomeric mold
Critical
aspect ratio
PDMS
distortion
Cl
OTS: Cl Si (CH2)17 CH
Cl 3
Hydrophobic SAM
Organic material
Hydrophobic
region
14
Micro-Contact Printing (CP) III
Direct... & additive
Substrate pre-treated with O2
plasma to imrpove idrophilicity
activating OH- groups Pentacene TFTs:
PEDOT S/D contacts,
W/L=140m/2m
Example 2.
Patterned LBL deposited
Film grown by LBL technique onto the PDMS mold
Organic Active Material
J.R. Tischler et al., Org. Elec. 8,94113, 2007.
15
Micro-Contact Printing (CP) V
Direct... & subtractive
C. Packard et al., Langmuir 2011, 27, 90739076
Applicable also to evaporated/solid films!
Test with oxygen plasma
Patterning mechanism?
Controllable thickness,
depending on contact time
Nanometer-scale accuracy of
thickness control!
16
Micro Transfer Molding
A liquid polymer precursor is poured in the cavities of the elastomeric
mold, put in contact with the substrate and finally cured.
Polymer must not shrink too much after curing
Whitesides et al., Angew. Chem. Int. Ed. 1998, 37, 550 -575
Whitesides et al., Angew. Chem. Int. Ed. 1998, 37, 550 -575
Pisignano et Al., Adv. Mater. 14, 1565, (2002)
17
Micro Molding in Capillaries II
EXAMPLE 1 EXAMPLE 2
FEATURES Ag nano-
300nm dispersion
(AFM image)
A. Blumel et al.,
Examples: Organic Electronics
8, 389395, (2007)
PEDOT:PSS as S/D
contacts in all
organic TFTs
H. Kang et al., Organic
Electronics 10, 527531,
(2009)
T>Tg
Tg: polymer
glass phase
transition
18
Nano Imprint Lithography/Embossing II
Example. Nanometer-sized electrodes for OTFTs
Silicon stamp
- Nanoimprint of photoresist (a,b,c)
- Dry etching in O2 plasma (d)
- Metallization Au/Ti (e)
- Lift-off in acetone (f) O2
d
100 nm
Physical Delamination
Based on a photolithographic process previous to semiconductor deposition
19
Photopatterning
Same principles of standard photo-lithography
resist is the active material!
UV Mask
Active material
Etching (solvent)
UV-Crosslinkable
Feature
size 5 m
Non-soluble materials:
deposition techniques
20
Vacuum Thermal Evaporation I
Sublimation of small molecules due to high-vacuum and high temperature
Substrate holder
PC on
thermal
Pentacene SiO2
on SiO2
PC on
Dimitrakopoulos, sputtered
Adv. Mater., 14,
palladium
99, (2002)
21
Organic Vapor Phase Deposition
Based on low pressure carrier gas instead of high vacuum
Deposition regimes
Equilibrium limited: Transport limited:
Substrate kept at a temperature Substrate at room temperature
high enough to establish an
adsorption/desorption equilibrium Better morphology
22
OVPD: examples
TFT based on Pentacene TPD-Alq3 OLED heterostructure
Alq3
Shtein et al. Appl. Phys. Lett., 81, No. 2 (2002) Forrest et Al., Appl. Phys. Lett., 71 (21), (1997)
10-9 mbar
Pin hole
pH ,TH
Effusion cell
(Knudsen) Shutter
23
Non-soluble materials:
patterning techniques
Shadow masking
Vapor Jet Printing
Shadow masking
Shadow mask (same principle of screen printing).
Resolution limited to tens of m.
24
Organic Vacuum Jet Printing (OVJP)
Organic small molecule material carried by hot inert gas to a nozzle
array that collimates the flow into jets
N2 flow rate
x=feature size
substrate-nozzle distance
25