Polarisation-dependent Raman spectroscopy as a probe of molecular orientation in organic thin films

Alina Zoladek-Lemanczyk1, Jong Soo Kim2, Ji-Seon Kim2, Fernando A. Castro1

Materials Division, National Physical Laboratory, Hampton Road, Teddington TW11 0LW, United Kingdom 2 Department of Physics & Centre for Plastic Electronics, Imperial College London, London SW7 2AZ, United Kingdom
1

Introduction
Molecular orientation can play a critical role in determining the optical and electronic properties of organic semiconductor thin films resulting in anisotropic energy levels and charge mobility. Therefore the ability to understand and quantify the molecular alignment of functionalized materials and conjugated polymers within thin-film samples is essential for a complete picture of their optical and transport properties for the continuous development of optoelectronic device applications. Polarization-dependent Raman microscopy is a powerful technique to perform both structural and chemical analyses with submicron spatial resolution. Raman data can also be collected in situ, which makes this technique even more attractive as a non-invasive device probe. We report here Raman polarisation measurements as a probe of molecular orientation in zone casted organic thin films.

Experimental and results

Figure 1. Schematic representation of polarised Raman spectroscopy on TIPS-Pentacene molecule. Spectra with strong Raman peak associated to short (blue) and long (red) axis of the pentacene backbone C-C- ring stretch are shown in conjunction with corresponding peak intensity versus polarisation graphs.

Film deposition via zone casting

TIPS-PEN(6,13-bis(triisopropylsilylethinyl) pentacene), PTCDI(3,4,9,10-perylenetetracarboxylic-diimide) and PBTTT(Poly(2,5-bis(3hexadecylthiophen-2-yl)thieno[3,2-b]thiophene)) thin films were deposited using zone-casting. This deposition method can induce molecular orientation by controlling the evaporation condition of the solvent. During evaporation, the molecules become less mobile and begin to order in the meniscus, where the solution makes contact with the substrate. Temperature of substrate/ solution and velocity of film deposition/solution release in zone casting machine are critical parameters. Spectra obtained from the zone casted TIPS-PEN film are shown in Figure 1. Spectra associated to C-C ring stretch modes for different axis of the pentacene backbone are presented. Short axis spectrum is in blue, while spectrum linked to the long axis is in red. In addition, corresponding polarisation graphs obtained from TIPS-PEN film are presented. Polarized Raman was also used to probe the molecular orientation of PTCDI films. The C-C stretch (Figure 2) and C-H stretch modes were used to investigate the anisotropic response and link it to molecular orientation. PBTTT is a polymer known to present liquid crystalline behaviour. Spin cast films do not present anisotropic behaviour. However, we observed strong polarisation dependence of the C=C Raman stretch mode, when measuring zone casted films annealed at 275 oC (Figure 3).

Polarised Raman Spectroscopy

Raman spectroscopy is an optical technique used to study vibrational modes of molecules, providing chemical information of the sample. It relies on the inelastic scattering of monochromatic light, therefore resolution is diffraction limited achieving spot sizes of ~300nm (laser wavelength dependent). Polarised Raman (p-Raman) spectroscopy probes additional information because it is sensitive to the molecular ordering and symmetry of sample components. p-Raman measurements are made acquiring spectra with polarisation which is either parallel or perpendicular to the inherent polarisation of the excitation laser. The incident light is plane-polarised and a polarisation analyser is used to measure the depolarisation ratio of the scattered light. In this way the isotropy and molecular alignment of a sample can be measured [2]. This application is of particular interest for investigations of thin-film nanomorphology since molecular alignment and packing are crucial for charge mobility. Polarized Raman spectroscopy was used to analyse the anisotropy and molecular orientation of zonecasted films using a Horiba LabRam HR Evolution 800 system. Excitation at 785 nm was chosen to avoid fluorescence and sample degradation.

Figure 2. PTCDI spectrum with Raman peak associated to C-C stretch mode. Inlet picture shows optical image of the sample. Additionally corresponding graph of peak intensity versus polarisation is presented.

Figure 3. PBTTT spectrum with Raman peak associated to C=C stretch mode. Inlet picture shows optical image of the sample. Additionally corresponding graph of peak intensity versus polarisation is presented.

Conclusion
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Polarised Raman spectroscopy has been used to characterise anisotropy of organic thin films and to allow correlation with molecular orientation. It is particularly suited to the investigation of conjugated polymer thin films, as they have phonon modes associated with -* transitions which have a particularly large Raman cross section [1]. Further work will focus on correlation between p-Raman, polarised near edge X-ray absorption spectroscopy and transistor characteristics.

Acknowledgements This work was funded through the European Metrology Research Programme (EMRP) Project IND07 Thin Films. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union.

References
1. 2. 3. 4. Kim, J.S., et al., Nature of non-emissive black spots in polymer light-emitting diodes by in-situ micro-Raman spectroscopy. Advanced Materials, 2002. 14(3): p. 206-+. Liem, H.M., et al., Raman anisotropy measurements: An effective probe of molecular orientation in conjugated polymer thin films. Advanced Functional Materials, 2003. 13(1): p. 66-72. Yim, K.-H., et al., Phase-Separated Thin Film Structures for Efficient Polymer Blend Light-Emitting Diodes. Nano Letters, 2010. 10(2): p. 385-392. Kim, J.S., et al., Electrical degradation of triarylamine-based light-emitting polymer diodes monitored by micro-Raman spectroscopy. Chemical Physics Letters, 2004. 386(1-3): p. 2-7

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