Deposition and patterning

techniques for Organic

Semiconductors

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

Vacuum Thermal Evaporation Shadow masking

Organic Vapor Phase Vapor Jet Printing
Deposition (OVPD)
Organic Molecular Beam
Deposition (OMBD)

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

Substrate Substrate Substrate

Film thickness: solution concentration

X Limitations in large area coverage
Very simple
X Thickness hard to control
No waste of material
X Poor uniformity

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,

Good uniformity/reproducibility X Waste of material

Good control on thickness X No large area
X Film dries fast
Easy to obtain film of 10nm or less less time for molecular ordering

Tricks...
McCulloch et Al., 180C
Thermal annealing
Nat. Mater., 5, 328, (2006)
(post-deposition)

Solvent evaporation time

Chang et Al.
Chem. Mater.,16, 23, (2004)
P3HT-based TFTs

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

It does not take into account

solvent evaporation

3
 Spin Coating III
Film thickness:
evaporation
flow dominated dominated

viscous flow rate = evaporation rate

1 1 1
hFIN c0 (1 c0 ) 3
2
( 0 ) 3 c(t)= solids concentration
(t)
most common reported experimental relationship
between thickness and rotation speed

D. E. Bornside, C. W. Macosko and L. E. Scriven, "Spin Coating of a

PMMA/Chlorobenzene Solution", J. Electrochem. Soc., 138, 317 (1991)

How to handle multilayer deposition?

Post-deposition film insolubilization
Thermally
Polymer cross-linking activated
UV-light
Cross-linked polymer chains Host cross-linkable polymer

Stable, high degree of control Appliable to any kind of polymer

X Polymer intrinsic properties are (small molecule?)
affected Doesnt affect polymer intrinsic properties
X Less deterministic
X Film properties are affected
P. Keivanidis et al., Binda et al.,
Appl. Phys. Lett. 94, 173303, 2009. Appl. Phys. Lett. 98, 073303, 2011.

4
Doctor Blading I
Spreading through a moving blade onto a stationary substrate
stationary moving

Large area X Micrometric precision of blade regulation

No waste of material
Good uniformity film thickness > 150200nm

Example. bladed organic solar cells (P3HT/PCBM)

W.-B. Byun et al. / Current Applied Physics 11 (2011)
Doctor bladed active
material in comparison with
spin-coated (~200nm)

Doctor Blading II
Film thickness:

Theoretical height of the wet layer thickness:

surface tension, wetting, viscosity, coating speed,...
Y. Chou, Y. Ko, M. Yan, J. Am. Ceram. Soc., 7010, 1987.
A.I.Y Tok, Journal of Materials Engineering and Performance, 8, 4, 1999.

sol h02 P U=blade speed

FilmThick ness h0 1
film 6 UL
=fluid viscosity
L=channel length
=density
ho=blade height
P=slurry pressure head

5
Doctor Blading refinement I:
zone casting
Controlled orientation of deposited layers

Controlled Deposition of Crystalline

Organic Semiconductors
Z. Bao, Adv. Mater. 21, 12171232, 2009.

by suitably controlling solvent

evaporation rate and solution supply
Optical TEM
microscope directional crystallization

substituted hexabenzocoronenes (HBCs)

Doctor Blading refinement II:

solution-sheared deposition

Z. Bao, Adv. Mater. 21, 12171232, 2009.

Diluited solution
Pre-heated substrates
Top wafer lyophobic

Fast evaporation of the front

produces a seeding film with crystal
grains that act as nucleation sites
TMS-4T dbo-P2TP

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)

Quite good uniformity X Waste of material

Very thin layers X Time consuming
Large area coverage X Double side coverage

Example: TFT based on P3HT in xylene single monolayer 2 nm thick

Sandberg et Al., Langmuir, 18, 26, 2002.

Extreme thickness control:

Langmuir-Blodgett film I
based on hydrophobicity/hydrophilicity

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]

KSV Instruments Application Note: http://www.ksvltd.fi/Literature/Application%20notes/LB.pdf

Extreme thickness control:

Langmuir-Blodgett film III
hydrophilic substrate
Movable barrier
Wilhelmy plate:
measures P

Feedback

Head-to-tail Tail-to-tail Head-to-head

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

Example. C60 dendrimer n-type TFT

LB film:
Polar 5 layers 15nm

Higher mobility than

spin-coated film
higher morphological
order
Apolar
Kawasaki et al., Appl. Phys. Lett. 91, 243515, 2007.

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

Adjustable layer thickness X Homogeneity of the film

Large area coverage
Independence on substrate topology

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

Baklar et al. Adv. Mater. 2010, 22, 39423947

Applicable to NON-soluble materials
Solid, powdered material placed in a hot press and compressed well
below the melting temperatures of the species

Medium area X Thickness 1-200m

No waste of material
Good uniformity
Highly ordered films

10
Compression molding
Radial molecular flow during compression molding

Free-standing flexible film

Material anisotropy X-ray diffraction

Baklar et al. Adv. Mater. 2010, 22, 39423947

Solution processable materials:

patterning techniques
Screen printing
Soft Lithography
NIL/Embossing
Physical Delamination
Photopatterning

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

Mask Z. Bao et al., A. J. Chem. Mater. 9,

1299-1301, 1997.

Simple X Limited resolution: 50-100 m

X Waste of material

Shadow masking+selective wettability

Exploiting the difference in wettability between hydrophobic surfaces
and hydrophilic surfaces to make the patterns
Journal of Polymer Science B: Polymer Physics, 49, 15901596, 2011

Hydrophobic SAM (Self Assembled Monolayer)

UV-light damages the

ODTS film
PEDOT/PSS: conductive polymer from aqueous suspension

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

Micro Contact Printing (CP)

Micro Transfer Molding (TM)
Mold
Micromolding in Capillaries
(MIMIC)
Whitesides et al., Angew. Chem. Int. Ed. 1998, 37, 550 -575.

13
Micro-Contact Printing (CP) I
Stamping of an ink through the elastomeric mold

Printed material has to adhere to the substrate while

the interaction with the mold has to be minimal

Critical
aspect ratio

PDMS
distortion

Micro-Contact Printing (CP) II

Indirect... ... mediated by SAMs

Monomolecular layer modifies substrate chemical proprieties

~few nm and the wettability

Cl
OTS: Cl Si (CH2)17 CH
Cl 3

Hydrophobic SAM

Organic material
Hydrophobic
region

C. R. Kagan, Appl. Phys. Lett. 79, 3536, 2001

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

Baking step at 80C to

ensure chemical bonding
(an adhesive agent is added
to PEDOT:PSS solution)

D. Li and J. J. Guo, Appl. Phys.

Lett. 88, 063513, 2006.

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.

Micro-Contact Printing (CP) IV

Direct... & subtractive
As the stamp is placed in contact with a liquid thin film spread on a substrate,
capillary forces drive the solution to form menisci under the stamp protrusions

b) AFM image of the stamp; c) printed

Dilute solution Very dilute solution AlQ3 film using dilute solution; d) very
dilute solution; e) line profile of stamp and
Solution pinned to films
the edges Cavallini, Nano Lett., Vol. 3, No. 9, 2003.

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?

Lift-off due to adhesion forces PDMS

between polymer and stamp glass
stamp
before
Organic film removal due to organic molecules
diffusion into the PDMS stamp during contact
(suggested by time dependence of material removal)
glass PDMS
Molecules stimulated fluorescence stamp
after

Micro-Contact Printing (CP) VI

Direct... & subtractive
C. Packard et al., Langmuir 2011, 27, 90739076
Applicable also to evaporated/solid films!

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

Typical materials: polyurethane, polyacrylates and

epoxies
3D structures

A: polyurethane on Ag, Microstructures of

B,C,D: epoxy on glass glassy carbon

Whitesides et al., Angew. Chem. Int. Ed. 1998, 37, 550 -575

Micro Molding in Capillaries I

Based on the flow of a liquid in capillaries
Flow dynamics: Z: length of the liquid
column into the capillary
dZ R lv cos
2R
L dt 4Z
: liquid viscosity
Z lv: liquid-vapor surface energy
: liquid-capillary surface contact angle

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)

Polyurethane in PDMS mold

EXAMPLE 3

PEDOT:PSS as S/D
contacts in all
organic TFTs
H. Kang et al., Organic
Electronics 10, 527531,
(2009)

Nano Imprint Lithography/Embossing I

Similar to SL but based on hard mold/stamp. I
It allows obtaining smaller features ( 10 nm)

T>Tg
Tg: polymer
glass phase
transition

Hot Embossing Room Temperature NIL

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

Kam et al., Microelectronic Engineering,

73, 809813, 2004.

Physical Delamination
Based on a photolithographic process previous to semiconductor deposition

Optical and AFM images

Polymer adhere to the substrate
of patterned PBTTT
where OTS is not present
Sirringhaus, Adv. Mater., 21, 16, 2009.

19
Photopatterning
Same principles of standard photo-lithography
resist is the active material!
UV Mask

Active material

Etching (solvent)
UV-Crosslinkable

Example: patterning of pixel in OLED display:

Patterning of the hole transport layer

Feature
size 5 m

Nuyken et Al., Macromol. Rapid Commun., 25, 11911196, 2004.

Non-soluble materials:
deposition techniques

Vacuum Thermal Evaporation

Organic Vapor Phase
Deposition (OVPD)
Organic Molecular Beam
Deposition (OMBD)

20
Vacuum Thermal Evaporation I
Sublimation of small molecules due to high-vacuum and high temperature

Substrate holder

Pressure 10-5-10-7 torr Molecules mean free

path: tens of cm - m
Evaporated molecules travel in
straight lines inside the chamber
and they condense on the
Source boat: substrate
contains the material
and it is heated at Growth rate controlled by tuning
hundreds of C the temperature of the source
boat

Thickness of the film is monitored with the crystal microbalance

(change of the resonating frequency of a piezo resonator).

Vacuum Thermal Evaporation I

Growth rate and substrate temperature affect film morphological order

PC on
thermal
Pentacene SiO2
on SiO2
PC on
Dimitrakopoulos, sputtered
Adv. Mater., 14,
palladium
99, (2002)

High quality, ordered thin films X Waste of material

Good control and reproducibility of
film thickness
Multilayer deposition and co-
deposition of several organic
materials
X Expensive equipments
X Very low throughput
high production costs
X No large area coverage

21
Organic Vapor Phase Deposition
Based on low pressure carrier gas instead of high vacuum

Hot inert carrier gas (Ar, N2)

transport source material to
the cooled substrate where
condensation occurs

Heated walls vapor

does not condense

OVPD: working regimes

Evaporation regimes

Equilibrium evaporation: Kinetic evaporation:

Organic evaporation limited by Organic evaporation limited by
the evaporation rate the flow of the carrier gas

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

SiO2 SiO2-OTS TPD

Alq3

Shtein et al. Appl. Phys. Lett., 81, No. 2 (2002) Forrest et Al., Appl. Phys. Lett., 71 (21), (1997)

Advantages over standard VTE:

Higher deposition rates
Less waste of material (no condensation on the internal walls)
Better film thickness control and uniformity in large area substrates

Organic Molecular Beam Deposition

Flow of focalized molecules in ultra high vacuum
Quartz
Substrate microbalance
Extremely slow deposition rate epitaxial growth
pC ,TC Single crystal

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.

Patterning of RGB sub-

pixels in OLED displays

Fukuda et Al., Synthetic Metals,

111112 (2000)

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

Condensation onto a proximally located

cold substrate, that can moove relatively
to the print-head for patterning

For high resolution (~20m):

Narrow nozzles ~10m
Low gas flow rate

Fabricated by MEMS processing

G.J. McGraw, Appl. Phys. Lett. 98, 013302, 2011.

Organic Vacuum Jet Printing (OVJP)

6 tubes with different
Fluorescence from Alq3 stripes
source material

N2 flow rate

x=feature size

substrate-nozzle distance

25