TOWARDS THERMALLY STABLE POLY (3-HEXYLTHIOPHENE) BASED PHOTOVOLTAIC DEVICES

NAUMAN MITHANI CHEM 481 Supervisor: DR. STEVEN HOLDCROFT Term 1104

INTRO: need for alternative/renewable energy

eventuality

economics smog greenhouse extreme weather

INTRO: energy consumption forecast

Source: Arvizu, D; National Renewable Energy Laboratory: Milken/Sandia workshop for financial & capital market leaders, 2007/10/23.

INTRO: photovoltaic materials - organic vs. inorganic

lightness of weight flexibility

large scale low cost

printability / substrate flexibility molecular engineering band gap control

lower efficiency

poorer stability
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INTRO: choice of organic materials efficiency & promise

organic photovoltaic materials -conjugated polymers P3HT & PCBM *

poly (3-hexylthiophene) (P3HT) donor (D) / hole carrier

[6,6]-phenyl C61 butyric acid methyl ester (PCBM) acceptor (A) / electron transporter
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* Yao, Y.; Hou, J.; Xu, Z.; Li, G.; Yang, Y. Advanced Functional Materials 2008, 18, 1783.

INTRO: mechanism of photo (photon) voltaic (charge)

exciton generation

diffusion to interface

exciton dissociation

INTRO: mechanism of photo (photon) voltaic (charge)

{contd.}

free electron/hole pairs

charge transport photocurrent

INTRO: the mish-mash OR bulk heterojunction (BHJ)

bulk heterojunction:
an inter-penetrating, bi-continuous (binary), nano-scale network of donor/acceptor (D/A) domains

scale of exciton diffusion is (tens of) nanometres exciton must reach interface in <20 nm BHJ advantages: large/widespread D/A interface on nm scale viable exciton dissociation bi-continuous (binary) network continuous, separate pathways for electrons/holes
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INTRO: prelude to project

P3HT & PCBM blend P3HT & PCBM are ultimately immiscible 10 m

eventual microscopicscale phase segregation (103 over limit)

interruption of bi-continuity (discrete aggregates)

P3HT-(graft-PCBM) & PCBM blend Thermal annealing: some PCBM post-functionalised onto P3HT serves to tether some PCBM to P3HT

100 m

serves as accelerated lifetime evaluation of (thermal) stability

annealing duration/temp. must be optimised to avoid phase segregation excess post-functionalisation interruption of P3HT chains self-organisation & semi-crystallinity

decrease in electron hole mobility

performance & stability bi-continuity & semi-crystallinity

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 9

EXPT.: synthesis of poly 2%(3-bromo-4-hexylthiophene), 1

NBS (2% by mole)

P3HT
98% regioregular (H-T)

where extent of post-functionalisation, n = 0.02

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 10

EXPT.: P3HT-2%(TEMPO-styrene) macroinitiator, 2

n = 0.02
Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 11

EXPT.: synthesis of P3HT-2%(graft-(ST-stat-CMS)), 3

nitroxide-mediated living radical polymerisation

n = 0.02

x:y = 1:1
Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 12

RESULTS & CHARACTERISATION: 1H-NMR of P3HT-2%(graft-(ST-stat-CMS)), 3

CMS:ST provided by
m:k

0.99 :

1.93 1:1 2

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RESULTS & CHARACTERISATION: aggregation of P3HT-2%(graft-(ST-stat-CMS)), 3

UV-Vis spectra of 3 in CHCl3

Polymer aggregation induced by MeOH

max of P3HT backbone shifts from 452 nm to 530/570 nm -* stacking of the

P3HT chains
occurrence of vibrionic side bands semi-crystalline 2% graft density is acceptable towards P3HT self-organisation arrangement of chains

long-range -conjugation (hole mobility) is NOT hampered

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EXPT.: synthesis of P3HT-2%(graft-(ST-stat-N3MS)), 4

n = 0.02

x:y = 1:1
Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 15

EXPT.: blend of P3HT-2%(graft-(ST-stat-N3MS)) + PCBM (1:1)

free PCBM

Step 1:

&

Step 2:

spin-coat on quartz substrate slow evaporation

bulk heterojunction

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708.

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EXPT.: 1:1 blend of P3HT-2%(graft-(ST-stat-(NMS-graft-PCBM))) + PCBM

blend of

in excess relative to number of reaction sites on 4

free PCBM grafted PCBM

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 17

RESULTS & CHARACTERISATION: optical microscope photographs of blend, pre- & post-annealed
pre-annealed graft copolymer blend post-annealed graft copolymer blend

1:1 P3HT+PCBM system

10 m

discrete PCBM aggregates semi-crystalline P3HT domain

microscopic phase separation
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100 m

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708.

RESULTS & CHARACTERISATION: UV-Vis spectra of blend, pre- & post-annealed

PCBM abs. P3HT abs.

pre-anneal: P3HT max blue-shifts

from 525 nm to 500 nm -* stacking of the P3HT chains is hindered post-anneal: P3HT max appears to be less blue-shifted -* stacking of the P3HT chains is less hindered

same relative intensity of vibrionic side-bands to abs. maximum suggests semi-crystalline

arrangement still occurs

Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Polymer Chemistry 2010, 1, 708. 19

CONCLUSION
1:1 P3HT(copolymer) + PCBM blends do NOT suffer microscopic phase separation

Thermal annealing was successful: greater degree of self-organisation of P3HT

as shown by red-shifting in UV-Vis spectra relative to pre-annealed blends temperature of 150 oC and duration of 1 hr. are acceptable P3HT(copolymer)+PCBM blends exhibit thermal stability

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FUTURE WORK
Photoluminescence spectroscopy: better understanding of SPR such as electron hole formation efficiency by PL quenching

Addition of high boiling point additive e.g. 1,8-octanedithiol* to solution in film-casting: selective
dissolution of PCBM
enhanced solubility of PCBM uniform film formation, no spots of insolubility

Detailed morphology study by Transmission Electron Microscopy: determination of P3HT(copolymer) and PCBM domains, and changes after annealing Photovoltaic performance parameters: hole mobility, current density vs. potential, external quantum efficiency (EQE) and overall power conversion efficiency (PCE) Optimisation of blend ratio
quantitative analysis by Thermo-gravimetric analysis (TGA) & NMR

*Lee, J. K.; Ma, W. L.; Brabec, C. J.; Yuen, J.; Moon, J. S.; Kim, J. Y.; Lee, K.; Bazan, G. C.; Heeger, A. J. Journal of the American Chemical Society 2008, 130, 3619.

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ACKNOWLEDGEMENTS
Bobak Gholamkhass Dr. Steven Holdcroft
Dr. Timothy Peckham Dr. Mahesh Kulkarni Dr. Jaclyn Brusso

Kristen Soo
Graeme Suppes Owen Thomas Martyn Stocker Jessica Luo Emily Tsang Ami Yang
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Fin