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Documenti di Professioni
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in organic electronics
Michael Toney
Synchrotron Materials Sciences Division
Stanford Synchrotron Radiation Lightsource (SSRL)
SLAC National Accelerator Laboratory
http://www-ssrl.slac.stanford.edu/toneygroup
Ed Kramer
8/5/1939 - 12/27/2014
Outline
1. Organic Electronics Thin Films
Wide range of length scales
2. Quantitative Molecular Packing
Small molecules Pentacene (&TIPS-Pentacene)
Polymers PBTTT
3. Nanoscale (dis)order - lattice variations, grains
Paracrystallinity
4. Organic Photovoltaics (OPV) Blends
nm-scale blend morphology
5. Summary
SSRL
Few other labs in the world currently hosts such a unique and
comprehensive suite of x-ray sources and instrumentation
5
Organic Semiconductors
GE
OLEDs
OFETs
Displays
Lighting
Display Backplanes
RFID Tags
Memory
Logic
Sony
PolyIC
OPV
Plastic Solar Cells
6
Organic Semiconductors
Ease of processing:
Organic Semiconductor Materials
Small Molecules:
Pentacene,
TIPS-Pentacene
semiconducting inks
printing - i.e. newsprint
low temperature deposition
ambient pressure
Unique Opportunities:
Polymers:
P3HT
PBTTT
Flexible substrates
Large area/High throughput
Chemically tailor properties
Sensing capabilities
Biocompatible
Organic Semiconductors
Transistors (OFET)
poly-Si
Photovoltaics (OPV)
Organic Semiconductors
Design Rules for New Functional Organic Electronics
Chemistry &
Processing
Performance
transistors
photovoltaics
Physical
Microstructure
OPV
OFET
Rivnay, Mannsfeld, Miller, Salleo, Toney, Chem. Rev. 112, 5488 (2012).
10
Outline
1. Organic Electronics Thin Films
Wide range of length scales
2. Quantitative Molecular Packing
Small molecules Pentacene (& TIPS-Pentacene)
Polymers PBTTT
3. Nanoscale (dis)order - lattice variations, grains
Paracrystallinity: Warren Averbach
4. Organic Photovoltaics (OPV) Blends
blend morphology
PBTTT:
5. Summary
Chad Miller
Pentacene
Stefan Mannsfeld
Zhenan Bao
Ajay Virkar
Colin Reese
Roman Gysel
Nicky Cates Miller
Alex Mayer
Mike McGehee
EK Cho
Chad Risko
Jean Luc Brdas
11
Pentacene Films
Pentacene:
Single crystal transistors on SiO2:
= 0.3 cm2/Vs
= 0.62 cm2/Vs
Q = (4
) sin
Pentacene Films
Pentacene (small molecule) films:
highly textured 2D powder
aligned out-of plane (001)
in-plane powder: random
orientation in substrate
(-1 2)
(0 2)
(1 2)
(-1 1)
(-2 0)
(1 1)
(-1 -1)
Qxy
(2 0)
(1-1)
b*
(-1 -2) (0 -2)
a*
(1 -2)
monolayer
(0 -2 L)
thin film
Qz
(11 L)
&
(1-1 L)
Qxy
c*
(12 L)
&
(1-2 L)
14
Pentacene Films
20 nm film
Qz
(1 1 L)
(1 2 L)
(0 2L)
(2 0L)
Qxy
a = 5.920 , b = 7.556 , c = 15.54
= 81.6 deg, = 87.2 deg, = 89.84 deg
15
Bragg peak
I (qhkl )
K- scaling factor
L- Lorentz factor
P- polarization correction
A- crossed-beam correction
D- Debye-Waller factor
T- Fresnel transm. coeff.
(1)
Monolayer films
Formula for intensity along Bragg rods:
I hk ( q z )
F (q )
Bragg rod
Atoms
qz ) |
(2)
4. Crystallographic refinement
Q. Yuan, et al, JACS. 130, 3502 (2008); Chem Matls. 20, 2763 (2008).
16
qz []
Observed
20 nm film
1.0
1.0
Calculated
0.8
0.8
0.6
0.6
55
0.4
0.4
0.2
0.2
0.0
0.0
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
substrate plane
2.4
qxy []
Observed
1.0
Calculated
60 nm film
0.8
0.8
q z []
18.5
1.0
b
0.6
0.6
0.4
0.4
a
0.2
0.2
0.0
0.6
0.0
0.8
1.0
1.2
1.4 1.6
qxy []
1.8
2.0
2.2
substrate plane
2.4
17
Pentacene Films
Pentacene sub-monolayer (nominal 1.5 nm, Tsub=60C) on SiO2.
Centered - Rectangular cell:
molecules vertical
a= 5.905 , b= 7.562
meas. I01(q Z)
calc. I01(q Z)
meas. I10(q Z)
calc. I10(q Z)
I(qZ) a.U.
meas. I11(q Z)
calc. I11(q Z)
meas. I02(q Z)
calc. I02(q Z)
meas. I12(q Z)
calc. I12(q Z)
2
1
0
0.0
0.1
0.2
0.3
-1
qZ [ ]
0.4
52
b
View down onto
substrate plane
substrate plane
18
19
Semi-crystalline Polymers:
P3HT, PBTTT
52
transport:
fast: (001) along chains
pretty fast: (010) along stacking
slow: (100) along alkyl chains
Brinkmann et al., Adv Mater. (2006)
20
Approach:
PBTTT C14
2D random GIXD -> initial structure via
modeling and GIXD simulation
biaxial textured films -> refine model
molecular mechanics (T = 0K)
McCulloch et al., Nat Mat. 5, 328 (2006).
Brocorens et al., Adv. Mater. 21, 1193 (2009).
Cho et al., JACS 134, 6177 (2012)
qz (A-1)
Semi-crystalline Polymers:
few (broad & overlapping) peaks
combine theory/modeling & experiment
qxy (A-1)
21
PBTTT structure
Out-of-plane orientation
Triclinic:
a = 21.5 ; b = 5.4 ; c = 13.5
= 137 deg; = 86 deg; = 89 deg
In-plane orientation
= 0 deg
24
b-axis
a-axis
PBTTT-C14
(meV)
th
114.65
te
138.72
th
0.00007
te
0.00002
25
Outline
1. Organic Electronics Thin Films
Wide range of length scales
2. Quantitative Molecular Packing
Small molecules - Pentacene
Polymers PBTTT
3. Nanoscale (dis)order - lattice variations, grains
Paracrystallinity
4. Organic Photovoltaics (OPV) Blends
blend morphology
Stanford
Jonathan Rivnay
Rodrigo Noriega
Leslie Jimison
Alberto Salleo
26
Brinkmann et al.,
Adv Mater. (2006)
crystallinity
pole figure (crystallite orientation distribution)
d-spacing (packing distance) variation
grain size
grain boundary structure grain size
27
disorder
e2
1/2
paracrystallinity
non-uniform strain
deviation from
mean d-spacing
within a grain,
and/or from one
grain to another
grain size
Less
More
28
Disorder/Strain
(little disorder)
200 nm
20 nm
5 nm
200 nm
20 nm
5 nm
Increasing disorder/strain
Decreasing grain size
30
qz [-1]
1.5
1.0
0.5
0.0
0.0
qxy
0.5
[-1]
1.0
31
diffraction along
lamellar stacking
-1
10
O
S
S
n
-2
P(NDI2OD-T2)
C8H17
H21C10
O N
10
O
C10H21
H17C8
-3
10
-4
10
0.2
0.4
0.6
b)
0.8
-1
1.2
1.4
Norm. Intensity
qz ( )
isolated peaks
-0.1
c)
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
0.1
q-qpeak ( )
32
1
0
normalized FT
10
Normalized A m(n)
0.8
Am(n)
Im (Q) exp
2 iQnd dQ
0.6
-1
10
0.4
0
0.2
10
15
Am (n)
P(NDI2OD-T2)
0
0
e)
10
12
14
16
d n
1 hkl e
M
m2 ng 2
m2 n 2 e 2
18
synthesized data
-0.1
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
q-qpeak ( )
0.1 -0.1
-1
0.1
q-qpeak ( )
33
qxy (A-1)
M.L. Chabinyc, JACS (2007)
Lamellar
Backbone
34
10
-2
(010)
10
10
H29C14
S
-3
H29C14
(020)
-4
S
S
qxy [A-1]
1
Normalized Intensity
0.8
Normalized An
result (pi):
o M = N/A
o g = 7.3%
o e = 0.9%
0.6
-0.8
0.4
-0.4
0
0.4
-1
qxy-qxy,peak [A ]
result (lamella):
o M = 25 nm
(large error bars)
o g = 2.0%
o e = 0.6%
0.8
Implications on transport?
0.2
10
15
20
25
n
36
Mobility:
strong dependence on overlap
& molecular packing
result (pi):
o M = N/A
o g = 7.3%
o e = 0.9%
37
50 -stacked
molecules
backbone (20 monomers)
delocalized
(0)
38
TIPS-Pentacene
In plane
[100] direction
10
10
-2
-4
1.5
2.5
-1
qxy ( )
Normalized Intensity
result [100]:
o M = 41 +/- 7 nm
o g = 0.9 +/- 0.6 %
o e = 0.1 +/- 0.1 %
PBTTT (pi):
o M = N/A
o g = 7.3%
o e = 0.9%
Normalized Am(n)
0.8
0.6
-.02
0.4
.02
-1
qxy-qxy,peak ( )
0.2
20
40
60
80
39
P3HT
PBTTT
PDPPBT
P(NDI2OD-T2)
IDT-BT
PCDTBT
r-Ra P3HT
PTAA
-1
~qz (-1)
semicrystalline
-2
3D amorphous
Summary + Outline
Organic thin film microstructure - local packing disorder:
distribution of packing (neighbor) distances - paracrystallinity
significant impact on charge transport
general observations:
polymers
g (sometimes e) is large
idea of grains may not be relevant
small molecules
g and e are small, grains can be large
44
q = (4 / ) sin
45
Additives:
DIO
ODT
ClN
C16
PDPP2FT:PC71BM 1:3
47
0.9%
P = 2.7
5.6%
48
blend blend
+ClN
blend
+DIO
blend
+ODT
Additive:
smaller domains & more intermixed domain interface
results in better exciton splitting and charge separation
Increased
Concentration
50
PDPP2FT in CB
Summary
1. Organic Electronics Thin Films
Wide range of length scales
2. Quantitative Molecular Packing
Small molecules Pentacene (&TIPS-Pentacene)
Polymers PBTTT
3. Nanoscale (dis)order - lattice variations, grains
Paracrystallinity
4. Organic Photovoltaics (OPV) Blends
Blend Morphology
53
Thanks
www-ssrl.slac.stanford.edu/toneygroup/
SSRL (SLAC)
Christopher Tassone
Kristin Schmidt
Chad Miller
Stanford University
Zhenan Bao
Mike McGehee
Alberto Salleo
NIST
Joe Kline, Dean DeLongchamp
KAUST
Pierre Beaujuge & Jean Frchet
GaTech
Jean Luc Brdas
54
Backup
Michael Toney
q = (4 / ) sin
56
Conclusion
Conclusion
Additives lower the nucleation barrier for polymer crystallization already in solution
leading to a higher nuclei concentration
Additives stabilize PCBM aggregates in solution
less substrate effects as crystallization starts in solution leading to a mixed
orientation of crystallites
faster crystallization kinetically traps the system resulting in smaller and more
intermixed domains
Additives give polymer mobility over a prolonged film drying process
increased coherence length and crystallinity
w/o additives:
w/ additives:
Michael Toney
Microstructure
GIXS
P3HT structure:
(h00):
slow
(00l): fast
(0k0): fast
bad - OPV
Qz
Qxy or Q
good - OPV
59
Mechanism
Organic Semiconductors
Small Molecules
Polymers
Something on performance
6
1