In modern electronics, it is essential to create almost arbitrary band structures by adjusting the energy bands and the band gap. Until now, band structure engineering in organic semiconductors has not been possible, since they usually exhibit localized electronic states instead of energy bands. In a recent publication [1], we showed that it is possible to continuously shift the ionization energy (IE) of organic semiconductors over a wide range by mixing them with halogenated derivatives. This tuning mechanism is based on interactions of excess charges with the mean quadrupole field in the thin film.
In this work, we raise the question whether the band structure engineering concept can be generalized to other organic semiconductor materials and even be used to tune the size of the band gap. As a model system we study oligothiophenes and in particular we address questions not only about the energy landscape, but also about the micro-structure and the molecular mixing in the film. For this purpose, we analyze optical measurements as well as photoelectron spectroscopy measurements of single and blended layers.
Reference:
[1] M. Schwarze et al., Science 352, 1446 (2016)
Diketopyrrolopyrrole polymers (DPP’s) are an important class of donor materials for organic solar cells owing to their supreme charge carrier mobility and optical absorption which extends into the NIR (until 950-1000 nm). The former allows making efficient solar cells with rather thick active layers while the latter makes them a good candidate to be used in tandem devices. In this study, we synthesized four different DPP polymers with thiophene and thienothiophene conjugation segments in the backbone. For each of the backbones, we changed the branching point of the solubilizing alkyl chains (at 2nd or 6th carbon position). Solar cells were fabricated in the inverted configuration under ambient conditions following the device architecture: ITO/PEIE/active layer/MoOx/Ag. In general, thienothiophene based polymers performed better yielding maximum PCE’s close to 6.5 %. Interestingly, the short-circuit current varied from 7mA/cm2 to around 18mA/cm2 for the best performing system. The morphology was investigated using TEM and grazing incidence wide angle x-ray scattering (GIWAXS). While - stacking was not influenced by the conjugation segments, GIWAXS measurements reveal closer - stacking ( 3.5 Å) in polymers with farther alkyl branching (at 6th carbon position) as compared to polymers with branching at the 2nd carbon position (- stacking distance 3.6 Å). Alkyl lamellar spacing for branching at the 6th-position was 28 Å while for the 2nd- position lamellar spacing was 17 Å. Pole figures of the - stacking peak were calculated to get an idea about the distribution of crystallite orientation. For the thiophene substituted DPP’s most of the crystallites had face-on orientation while for thienothiophene substituted DPP’s, population of both face-on and edge-on crystallites were observed. By integrating the peak intensity as a function of polar angle, the relative degree of crystallinity (rdoc) was determined for the four polymer systems. TEM images revealed a fibrillar morphology for the four blended systems. The average polymer fibril width varied among the four polymer systems. For the thiophene-based DPP polymers, fibers widths were 35-50 nm (much larger than the typical exciton diffusion length 10nm). To study the effect of polymer fiber width and fiber purity on charge generation we measured fluorescence quenching in the blend films by selectively exciting polymer domains. To shed further light on phase purity of polymer fibrils, carbon/sulphur elemental maps were obtained using TEM. Overall, we try to correlate the effect of alkyl branching on the formation of mixed-phase morphology and how it affects the device performance.
Self-assembled monolayers (SAMs) of alkyl silane compounds have been used for modifying gate dielectrics surface
of organic field-effect transistors (OFETs) and they have frequently shown improvement of FET performances. In this
paper we deposited alkyl silane SAMs by simple spin-coating technique onto Si/SiO2 substrates. Spin-cast
octadecyltrimethoxysilane (OTMS) SAMs had ultra smooth crystalline surface and provided an excellent dielectric
surface for OFETs. In fact on the OTMS SAM treated dielectric, pentacene OFETs showed hole mobilities over 2.0
cm2/Vs and electron mobilties over 1.0 and 5.0 cm2/Vs were demonstrated for 3,4:9,10-perylene diimide derivative and
C60, respectively. Fabrication technique and characterizations of the OTMS SAMs is described.
It has been well established that in organic thin film transistors (OTFTs), charge transport occurs within the first few
monolayers of the semiconductor at the semiconductor/dielectric interface. Understanding and engineering the
semiconductor-dielectric is therefore critical. Large discrepancies in performance, even with seemingly identical surface
treatments, indicate that additional surface parameters must be identified and controlled in order to optimize OTFTs.
Here, we used the Langmuir-Blodgett technique to study the effect of an octadecylsilane dielectric modification layer on
OTFT performance. We found a crystalline, dense OTS monolayer promotes two-dimensional growth in a variety of
organic semiconductors. Mobilities as high as 5.3 cm2/Vs and 2.2 cm2/Vs were demonstrated on crystalline OTS for
C60 and pentacene, respectively. Finally, we also developed a simple, scalable spin-coating method to produce crystalline OTS. This work represents a significant step towards a general approach for morphological control of organic
semiconductors which is directly linked to their thin film transistor performance.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.