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Polymer Self-assembly on Carbon Nanotubes

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Self-Assembly of Nanostructures

Part of the book series: Lecture Notes in Nanoscale Science and Technology ((LNNST,volume 12))

Abstract

This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV–Vis and Raman), we show how the polymer’s higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT π–π stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

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Notes

  1. 1.

    The multi-wall nanotubes reported in Palaci’s study had external radii ranging from 0.2 to 12 nm and constant R ext/R int ratio of 2.2 ± 0.2 nm; in the reported case, the external radii are 6.5 and 8.75 nm and the R ext/R int ratio is 2.23 and 2.46.

  2. 2.

    The value provided for the Young’s modulus of P3HT has been measured for polymer films. The authors believe that the tensile strength of the single polymer backbone can be higher, confirming the possibility of carbon nanotube deformation by P3HT strands.

  3. 3.

    It must be noticed that a charge migration from the nanotube to the polymer could have supported upshifts higher than expected, but would have failed to explain the relative downshift at higher polymer contents.

  4. 4.

    Although thermal annealing can enhance the polymer crystallisation order, Raman spectra collected on pristine P3HT samples before and after the thermal treatment did not show any downshift. This confirms that the nanotube sidewall structure can act as template to promote a more ordered polymer phase.

  5. 5.

    With high-energy electron beam is intended a radiation able to raise the temperature of the sample under analysis. Although there is no control of the temperature of the sample in the time frame under analysis, damages to the nanotube can be excluded. The damage of the sample occurred after a long-time exposure (not shown).

Abbreviations

°C:

Degree Celsius

AC:

Alternating current

AFM:

Atomic force microscopy

AR:

Analytical reagent

cm:

Centimetre

cm−1 :

Wavenumber

CNT:

Carbon nanotube

CuPc:

Copper phthalocyanines

CVD:

Chemical vapour deposition

DC:

Direct current

DOS:

Density of states

dTG:

Differential thermal gravimetry

DWNT:

Double-walled carbon nanotube

EQE:

External quantum efficiency

FWHM:

Full width half maximum

HOMO:

Highest occupied molecular orbital

HOPG:

Highly oriented pyrolytic graphite

HR-TEM:

High-resolution transmission electron microscopy

I sc :

Short-circuit current

ITO:

Indium tin oxide

LDOS:

Local density of states

LUMO:

Lowest unoccupied molecu lar orbital

MDMO-PPV:

Poly(2-methoxy-5-(3′,7′- dimethyloctyloxy)-1,4- phenylenevinylene)

MEH-PPV:

Poly[(2-methoxy-5-(2′- ethylhexoxy)-p-phenylene) vinylene]

mg:

Milligram

MIM:

Metal–insulator–metal

min:

Minute

ml:

Millilitre

mW:

Milliwatt

MWNT:

Multi-walled carbon nanotube

nm:

Nanometre

NP:

Nanoparticles

OPV:

Organic photovoltaic

P3HT:

Poly(3-hexylthiophene)

P3OT:

Poly(3-octylthiophene)

PCE:

Power conversion efficiency

PEDOT:PSS:

Poly(3,4-ethylenediox ythiophene):poly (styrenesulfonate)

PmPV:

Poly[(m-phenylene vinylene)-co-(2,5-dioctoxy- p-phenylenevinylene)]

PPV:

Poly(phenylenevinylene)

rr-P3HT:

Regioregular poly(3- hexylthiophene)

SCLC:

Space charge limited current regime

SEM:

Scanning electron microscopy

STM:

Scanning tunnelling microscopy

STS:

Scanning tunnelling spectroscopy

SWNT:

Single-walled carbon nanotube

TD-SCLC:

Trap-dominated space- charge-limited current regime

TEM:

Transmission electron microscopy

TF-SCLC:

Trap free space charge lim ited current regime

TG:

Thermogravimetry

TGA:

Thermogravimetric analysis

UHV-STM:

Ultra-high vacuum scanning tunnelling microscopy

UHV-STS:

Ultra-high vacuum scanning tunnelling spectroscopy

UV–Vis:

Ultraviolet–visible

V:

Volt

v :

Volume

V OC :

Open circuit voltage

w :

Weight

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Acknowledgements

The authors are thankful to Prof. M. De Crescenzi and Prof. J.M. Bell for helpful discussions and direction, Dr. E.R. Waclawik, Dr M. Scarselli, Dr. P. Castrucci, Dr. M. Diociaiuti, Dr. S. Casciardi for helping in the measurements and for their contribution to the discussions, Prof. J.C. Grossman, M. Bernardi for providing their expertise in the molecular dynamics calculations. The authors also acknowledge the financial support of the Queensland Government through the NIRAP project “Solar Powered Nanosensors.”

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    Michele Giulianini & Nunzio Motta

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Giulianini, M., Motta, N. (2012). Polymer Self-assembly on Carbon Nanotubes. In: Bellucci, S. (eds) Self-Assembly of Nanostructures. Lecture Notes in Nanoscale Science and Technology, vol 12. Springer, New York, NY. https://doi.org/10.1007/978-1-4614-0742-3_1

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