Role of structure and morphology

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

SLAC National Accelerator Laboratory

~1,700 employees + 3,400 users, visiting
scientists per year; 300 postdocs and
students; 75 PhD theses
Major DOE-BES scientific user facilities:
o Linac Coherent Light Source (LCLS)
o Stanford Synchrotron Radiation
Lightsource (SSRL)
Science Programs:
o Particle Physics & Astrophysics
o Accelerator Research
o Photon Sciences
Chemical and Materials Sciences
Sustainable Energy Materials
4

SLAC National Accelerator Laboratory

LCLS-offices

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

Conjugated bonding structure allows

for semiconducting properties
7

Organic Semiconductors
Transistors (OFET)

10-5 cm2/Vs (1980s) -> 20-30 cm2/Vs (2014) &

poly-Si

Photovoltaics (OPV)

Organic Semiconductors
Design Rules for New Functional Organic Electronics

Chemistry &
Processing

Performance
transistors
photovoltaics

Physical
Microstructure

How does structure affect performance?

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

Butko et al., Appl. Phys. Lett. 83, 4773 (2003).

= 0.1 - 0.5 cm2/Vs

Takeya et al., J. Appl. Phys. 94, 5800 (2003).

Polycrystalline thin film transistors on SiO2:

= 0.4 cm2/Vs

Klauk et al., J.Appl. Phys. 92, 5259 (2002).

= 0.62 cm2/Vs

Knipp et al, J.Appl. Phys. 93, 347 (2003).

= 1.0 - 5.5 cm2/Vs on other substrates

Film packing

bulk packing: Fritz et al., JACS 126, 4084 (2004).

Why do pentacene TFTs perform as good or better than

pentacene single crystal transistors?
12

X-ray Diffraction and Scattering

Q = (4

) sin

ACS Nano 6, 5465 (2012), JACS 134.,6337 (2012);

Advanced Materials 23, 127 (2011); Chem Rev 112, (2012)

Baker et al., Langmuir 2010, 26, 9146

13

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

(00Qz) (10Qz) (20Qz)

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

Pentacene Films structure refinement

Crystallographic refinement of diffraction intensities
1. Diffraction peaks
& intensities
Multilayer films

Bragg peak

2. Self-consistent indices and extract unit cell

3. Calculation of integrated intensities from theory
Necessary simplification:
assume rigid molecules. Reduces degrees of
freedom from 72 to 9 -> makes feasible
justified for fused-ring aromatic molecules.
Formula for Bragg peaks:

I (qhkl )

KLPAABCD D( qhkl ) | F (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

KLPAABCD Dhk ( qz )T2(q z ) | F ( qxy

fi exp(iqri )

Atoms

qz ) |

(2)

fi - atomic scattering factor

ri - atom position
q - momentum vector

4. Crystallographic refinement
Q. Yuan, et al, JACS. 130, 3502 (2008); Chem Matls. 20, 2763 (2008).

16

Pentacene Films Structure

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

View down onto

substrate plane

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

View down onto

substrate plane

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

Markus theory of electron transfer:

more overlap in monolayer
explains higher mobility
Mannsfeld, Virkar, Reese, Bao, Toney,
Adv. Mater. 21, 2294 (2009).

18

Tuning the structure

Solution Shearing to tune properties
TIPS-pentacene

G. Giri, .., M.F. Toney, Z. Bao, Nature 480, 504508 (2011)

19

Organic Thin Film Microstructure - Polymers

Semicrystalline polymers: partly crystalline & partly disordered
Small Molecules

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

PBTTT semiconducting polymer

PBTTT
poly(2,5-bis(3-tetradecyllthiophen-2-yl)thieno[3,2-b]thiophene)
high performance p-type semiconducting polymer

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

Miller et al., Advanced Materials 24, 607 (2012).

22

PBTTT GIXD & modeling

Approach:
2D random GIXD -> initial strcuture via modeling and GIXD simulation
biaxial textured films -> refine structural model

excellent agreement in peak positions Q= 0.68, 1.19, 1.35, 1.41, 1.71 -1

d(001) = 21.3 (MM) vs 21.5 (GIXD)
agreement with (H00) intensities
23

PBTTT GIXD & modeling

Approach:
2D random GIXD -> initial structure via modeling and GIXD simulation
biaxial textured films -> refine structural model
Q= 1.71 -1

(h10): Q = 1.71 -1 &

= 0 deg

24

PBTTT semiconducting polymer

Strong hole transport along the b-axis

B3LYP/6-31G**

Flat energy landscape:

many local minima
prevalence for disorder

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

Organic Film Microstructure

Semicrystalline polymers: partly crystalline & partly disordered

Brinkmann et al.,
Adv Mater. (2006)

Semicrystalline polymers: disorder

crystallinity
pole figure (crystallite orientation distribution)
d-spacing (packing distance) variation
grain size
grain boundary structure grain size
27

Microstructure: grains, packing disorder

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

local packing disorder: variation in

spacing between neighboring molecules

28

Diffraction Peaks & Disorder

Multiple diffraction orders: quantitative analysis of both disorder/strain & grain size
Grain Size

Disorder/Strain

(little disorder)

(20nm grain size)

200 nm

20 nm
5 nm

200 nm

20 nm

5 nm

Increasing disorder/strain
Decreasing grain size

grain size: width independent of order

disorder/strain: width dependent of

order (g and e different)
29

Diffraction Peaks & Disorder

analysis approach:
Fourier transform isolated diffraction peaks

A(L) Fourier coefficients product of finite

crystallite size & disorder terms

30

Diffraction Peaks: Warren-Averbach

P(NDI2OD-T2) = poly{[N,N 9-bis(2-octyldodecyl)-naphthalene-1,4,5,8bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bithiophene)}
stable, high performance n-type semiconducting polymer
2.0

qz [-1]

1.5

1.0

0.5

0.0

0.0

qxy

0.5
[-1]

1.0

31

Diffraction Peaks: Warren-Averbach

analysis approach:
Fourier transform isolated peaks
A(L) - crystallite size & disorder terms
a)

diffraction along
lamellar stacking

-1

Intensity (arb. units)

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

Diffraction Peaks: Warren-Averbach

d)

1
0

normalized FT

10

Normalized A m(n)

0.8

Am(n)

Im (Q) exp

2 iQnd dQ

0.6

Am (n) AS (n) Ame (n) Amg (n)

-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

result (lamellar direction):

M = 27 nm; 22 (14) nm, e = 1.7%, g = 3.6%
e)
Norm. Intensity

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

PBTTT: directional dependence

PBTTT = poly(2,5-bis(3-tetradecyllthiophen-2-yl)thieno[3,2-b]thiophene
qz (A-1)

high performance p-type semiconducting polymer

qxy (A-1)
M.L. Chabinyc, JACS (2007)

Lamellar

C. Wang, Adv. Mater 2010

Backbone

D. DeLongchamp, Adv. Mater 2011

34

PBTTT: directional dependence

D. DeLongchamp, Adv. Mater 2011

Joe Kline & Dean

DeLongchamp (NIST)
35

PBTTT: directional dependence

Intensity [a.u.]

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

PBTTT: directional dependence

Implications on transport?

Mobility:
strong dependence on overlap
& molecular packing

result (pi):
o M = N/A
o g = 7.3%
o e = 0.9%

V. Coropceanu, et al, Chem. Rev., (2007)

37

Packing Disorder - Transport

first principle simulation:
2D system DOS

20 sites along the backbone

50 -stacked molecules with varying g
disorder creates tail states
localized (Nt & E0)

50 -stacked
molecules
backbone (20 monomers)

delocalized
(0)

Increase in paracrystalline disorder produces

localized tail states in the bandgap
Rivnay, et al., Phys Rev B RC, (2011)

38

TIPS-Pentacene

In plane
[100] direction

Intensity (arb. units)

Packing Disorder small molecules

10

10

10

-2

-4

1.5

2.5

-1

qxy ( )
Normalized Intensity

FET 0.5-5 cm2/Vs

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

Organic Solar Cells: Morphology

Order in semicrystalline polymers:
packing disorder paracrystallinity (g)
semicrystalline (P3HT, PBTTT)
weak order (PCDTBT)
poor order -> amorphous
(rRA-P3HT)

Noriega et al., Nature Materials, doi:10.1038/nmat3722

40

Organic Solar Cells: Morphology

qxy (-1)
2

P3HT

PBTTT

PDPPBT

P(NDI2OD-T2)

IDT-BT

PCDTBT

r-Ra P3HT

PTAA

-1

~qz (-1)

semicrystalline

-2

3D amorphous

Order in semicrystalline polymers:

packing disorder - paracrystallinity
semicrystalline (P3HT, PBTTT)
weak order (PCDTBT)
poor order/amorphous (rRA-P3HT)

Noriega et al., Nature Materials, doi:10.1038/nmat3722

41

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

1. Organic Electronics Thin Films

2. Quantitative Molecular Packing
3. Nanoscale (dis)order - lattice variations, grains
Paracrystallinity
4. Organic Photovoltaics (OPV) Blends
blend morphology
42

Organic Solar Cells: Morphology

Three separate regions:
pure donor semicrystalline
some ( 20%) fullerene in amorphous donor
pure fullerene amorphous
Some issues:
Molecular packing in donor
polymer: carrier & exciton
transport
BHJ morphology (nm lengths);
close to exciton diffusion length
Intermixing of donor & acceptor
Interface structure
Gomez, et al. Chem Comm, 47, 436 (2011)
Treat, et al., Adv. Energy Mater. 1, 82 (2011).
Chen et al., NanoLetts. (2011).
43

BHJs: nanoscale phase segregation

Sizes of three separate regions:
pure donor
mixed fullerene-donor
pure fullerene

Need to combine several methods:

Imaging EF-TEM
Scattering (SAXS + R-SoXS)

44

Probe Morphology with Scattering

Transmission Scattering:
hard x-rays (films, solutions)
probe structures up to 50 nm
soft x-rays (films) probe
structures up to 1 m
solution SAXS

q = (4 / ) sin

Guinier - domain size (D)

Porod (P) exponent
interface roughness

45

Understanding the Porod Exponent

Porod (P) exponent:
shape of scatterers (particles)
interface roughness between domains

diffuseness of interface (fractal)

P= 4->3, more` mixed, jagged
P= 3->2, more loose, mixed
46

Improvements Using Additives - PDPP2FT:PC71BM

Five fold Efficiency Enhancement in PDPP2FT:PC71BM

Additives:

DIO
ODT
ClN

C16

0% ClN: PCE = 0.9%,

Jsc = -1.9, Voc = 0.69, FF = 0.65

5% ClN: PCE = 5.7%,

Jsc = -12.6, Voc = 0.65, FF = 0.69

PDPP2FT:PC71BM 1:3

Yiu et al., JACS 2012, 134, 2180

KAUST & UC-Berkeley

Alan Yiu
Jeremy Niskala
Olivia Lee
Pierre Beaujuge
Jean Frchet

47

Blend Structure of C16-PDPP2FT

PDPP2FT: PC71BM 1:3

P = 3.5

0.9%

P = 2.7
5.6%

48

Influence on Blend Microstructure

PDPP2FT: PC71BM

blend blend
+ClN

blend
+DIO

Additive leads to:

decrease in phase segregated domain
size: 100s nm -> 80 nm
more intermixed interfaces (smaller P)

blend
+ODT

Additive:
smaller domains & more intermixed domain interface
results in better exciton splitting and charge separation

Whats the mechanism behind these changes?

49

Structure of C16-PDPP2FT in solution

w/o additive in CB

no Guinier regime at low q

aggregates > 100 nm
no Gaussian behavior (P=3)
chains aggregate even at low
polymer concentrations
broad peak at high q & slope
of -1 appear with increasing
concentration
alkyl chains correlate leading
to longer stiff chain segments
formation of small nuclei

Increased
Concentration
50

Structure of C16-PDPP2FT in solution

PDPP2FT in CB

SAXS fullerene =>

no effect of additives
Weakly ordered polymer aggregates act as seed sites for crystallization
promotes a higher density of seed crystals

Film has better morphology

Schmidt et al. Adv. Mater. 2014, 26, 300.

51

Mechanism for C16-PDPP2FT

Weakly ordered polymer aggregates act as seed sites for crystallization
promotes a higher density of seed crystals

Film has better morphology

More jagged interfaces
Mixed crystallite orientation
Optimal length scale phase segregation

Schmidt et al. Adv. Mater. 2014, 26, 300.

52

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

Probing Solid State Film and Casting Solution

Solution SAXS

Solid State SAXS

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

Understanding the Porod Exponent

Porod exponent (fractal interface):
diffuseness of interface between
domains
P= 4->3, more mixed, jagged
P= 3->2, more loose, mixed
shape of particle

GIXS
P3HT structure:
(h00):
slow

(00l): fast

(0k0): fast

bad - OPV

Qz

Qxy or Q

good - OPV

59

Mechanism

Structure of C16-PDPP2FT in Solution

persistence length from

intersection of different slopes
additives lower the critical concentration
for stiff nuclei regions
stiff regions 25 nm
possibly - persistence length increases with
increasing polymer concentration &
additives
Michael Toney60

Organic Semiconductors

Small Molecules

Polymers

Something on performance

6
1