Fused Quinoidal Oligothiophenes Imides with High Electrical Conductivity

Organic diradicals are molecules containing two unpaired electrons, which are usually highly reactive.1-2 Although these organic diradicals present a wide range of potential applications, their air stability still remains as a major obstacle.3 In order to overcome this, new organic diradicals based on quinoidal oligothiophenes-derivatives (QOT) have been synthesized, i.e. BTICN, ISOCN and QTICN (see Figure 1). These new molecules present high stability and electrical conductivity, which have been achieved by employing imide-bridged fused molecular frameworks. The combination of strong electron-withdrawing imide with tetracyano groups in the conjugated skeletons also enabled extremely deeply aligned LUMO levels and large diradical character assisted by cross-conjugation.4 Here we use different experimental techniques and DFT calculations to provide new insights into the electron conduction mechanism of QOT diradicaloids, in order to demonstrate the great potential of fused quinoidal oligothiophene imides in developing stable organic diradicals and high-performance doping-free n-type conductive materials.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Analyzing thin film morphology by Resonance Raman spectroscopy

Polymeric organic thin film transistors (OFETs) and all-polymer bulk heterojunction solar cells (all-PCS), which are composed of a polymer donor and a polymer acceptor, have attracted considerable attention in the last years. The interest of these polymeric materials present various advantages versus small molecular counterparts, including strong light absorption, excellent mechanical flexibility and durability, and great potential in printing applications due to their great processability. In OFETs and bulk heterojunction solar cells, the morphology and crystallinity control of the neat polymer or blended donor-acceptor polymer films is essential in order to improve device performance. In this communication, we present a Resonance Raman spectroscopy study directed to disentangle the film morphology of a series of all-acceptor and donor acceptor polymers for OFETs and all-PCS applications.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Understanding charge transport in organic field effect transistors

The organic electronics research field has advanced tremendously in the last decades, having already led to field-effect mobilities able to compete with their inorganic counterparts. However, many fundamental aspects of this field remain still unclear and need to be clarified before its final blossoming, which would probably come with the complete understanding of the charge transport mechanism in organic materials. It is well-known that the performance of organic semiconductors is governed not only by their molecular structures but also by their intermolecular assembly in the solid state. Therefore, analyzing organic materials from both a molecular and supramolecular point of view is highly desirable. For this end, Raman spectroscopy is a rapid, non invasive technique able to gather information on molecular and supramolecular levels, thus being greatly useful in the organic electronics research field. Analyzing buried interfaces, such as the semiconductor-dielectric interface in organic field effect transistors (OFETs) is fundamental, since the largest contribution to charge transport occurs within the first few nanometers of the semiconductor near the dielectric interface. Surface Enhanced Raman Spectroscopy (SERS) appears as an easy and straightforward technique to carry out this task and to provide useful information on molecular orientation at the device active layer. In this communication, some examples will be presented in which several spectroscopic techniques, conventional Raman and SERS, supported by DFT quantum chemical calculations have been used to shed light on the mechanism of charge transport in OFETs.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Understanding the structure-property correlations of n-type organic semiconductors in OFETs

In the organic electronic research field, the development of high-performance unipolar n-type semiconductors is still challenging. Here we present an in-depth study of a series of ladder-type semiconductors, which due to their all-acceptor backbones, exhibit unipolar n-type transport in OTFTs. It is well know that the performance of organic semiconductors is governed not only by their molecular structures but also by their intermolecular assembly in the solid state. Thus, highly planar backbones are beneficial for a good molecular packing and film ordering leading to good charge transport characteristics. In this contribution, we study a series of BTI small molecules and polymers, both from a molecular and from a supramolecular point of view, in order to establish useful structure-property relationships that may guide the rational synthesis of new and improved materials. To carry out this study, we make use of different spectroscopic techniques, supported by quantum theoretical calculations at the DFT level.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Understanding polymer orientation at the interface by SERS

In the organic electronic research field, it is well known that the largest contribution to charge transport occurs within the first few nanometers of the semiconductor near the dielectric interface. Surface Enhanced Raman spectroscopy (SERS) appears as an easy and straightforward technique to analyze this buried interface and to provide useful information on molecular orientation at the device active layer. Here we present the study of the molecular orientation of the widely studied P(NDI2OD-T2) polymer at the semiconductor/dielectric and semiconductor/metal interfaces using SERS and DFT calculations. Our first SERS results show a relative intensification of selected normal modes, which indicates that the orientation of the polymer changes from a face-on (before annealing treatment) to and edge-on disposition after melt annealing, being this in good agreement with the previous results gathered from other techniques (Figure 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Transporte de carga de sistemas tipo escalera (ladder-type) en transistores orgánicos de efecto campo (ofets)

Las moléculas π-conjugadas tipo escalera con estructura plana están recibiendo un enorme interés como semiconductores moleculares o como unidades constituyentes de otro tipo de estructuras más grandes o polímeros para dispositivos electrónicos. Sin embargo, la mayoría de las moléculas de tipo escalera exhiben características de tipo p, siendo un gran desafío conseguir análogos deficientes en electrones. En este sentido, los arenos funcionalizados con imidas son materiales altamente prometedores. Entre ello, los bitiofenoimida (BTI) tipo escalera, presentan excelentes propiedades fisicoquímicas y electrónicas. Por ello, haciendo uso de técnicas espectroscópicas, cálculos químico-cuánticos DFT y caracterización eléctrica en transistores orgánicos de efecto campo (OFETs), establecemos en este estudio relaciones estructura-propiedad que nos ayudan a entender el transporte de carga de estos sistemas.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. RSEQ Sigma Aldric

SpectroscopicTechniques and DFT Calculations to Understand Charge Transport Mechinisms in OFETs

The organic electronics research field has advanced tremendously in the last decades, but there is still an incomplete understanding of the main mechanisms governing charge injection and transport in such devices. The performance of organic semiconductors is governed not only by their molecular structures but also by their intermolecular assembly in the solid state. Here we use a combination of Raman spectroscopy and charge modulation spectroscopy (CMS) to gather information on molecular and supramolecular levels, of organic semiconductors [1,2] (Figure 1) [3]. This last one is an optical-spectroscopy technique conducted on a real OFETs, that allows us to study in situ the charge carriers present at the semiconductor-dielectric interface, where the largest contribution to charge transport occurs. [3] In this communication we will present the study of the bithiophene imide (BTIn) molecules which exhibit encouraging electron mobilities in OFETs [1,2], by using the spectroscopic techniques presented above, supported by DFT quantum chemical calculations in order to shed light on the mechanism of charge transport in OFETs.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Electronic properties of Naphthalimide derivatives

Molecular systems have proven to be efficient active materials in electronics, making then suitable substitutes of the inorganic semiconductors used nowadays in electronic devices. For this reason, organic electronics has emerged as a research field with great potential and interest. In this project we have studied, both experimentally and theoretically, two ladder-type compounds functionalized with naphthalimides (Figure 1). The two molecular systems have been implemented in organic field effect transistors (OFETs), to assess their potential as active materials in organic electronics. Both compounds show p-type type mobility, moreover, NDI-TP-Ph-TP material also displays low n-type mobility, presenting a certain ambipolar character. The nature and stability of the charged species involved in the charge transport process have also been studied by spectroelectrochemical experiments.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Electronic Properties of Naphthalimide-based Ladder-type Systems

The tuneable electronic and structural properties of organic semiconductors together with their flexibility, light weight, high solution processing and low costs in comparison with inorganic semiconductors are some of the key points for the current interest in the development of π-conjugated small molecules and polymers for a variety of applications. In this project, a combined experimental and theoretical study of two ladder-type compounds functionalized with naphthalimides1 (Figure 1) is performed with the aim to explore the impact of the structure on the optical and charge-transport properties. Compound NDI-TP-Ph-TP has an imidazole group as a spacer ring and NIP-TP-Ph-TP has a spacer ring of pyrazine type. The two molecular systems have been implemented in organic field effect transistors2 (OFETs), to assess their potential as active materials in organic electronics. Both compounds show p-type mobility, moreover, NDI-TP-Ph-TP material also displays low n-type mobility, presenting a certain ambipolar character.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Tunable electroactive oligothiophene-naphthalimide semiconductors via end-capped engineering: cumulative effects beyond the linker

Aiming to obtain novel functional semiconducting materials for their use in organic electronics, the combination of strong donor moieties with electron-withdrawing units is one of the most useful strategies to obtain ambipolar semiconductors with tunable properties. Nowadays most of the efforts headed to efficient materials are based on small changes in the alkyl pendant chains or by replacing single atoms. However, a precise design of new functional materials is still challenging. For this reason, in this work we present a new synthetic approach for achieving redox amphoteric organic semiconductors by tuning their opto-electrochemical properties via rational chemical modifications. All these materials present low-lying LUMO levels, lower than −4.00 eV with broad absorption up to 800 nm in the UV-Vis-NIR spectra. In addition, they have been characterized by DFT, absorption and Raman vibrational spectroscopies, while their charge stabilization abilities are studied by means of spectroelectrochemical techniques. The results point out to a quite complex electronic scenario that goes beyond the expected cumulative effects of the independent molecular units constituting the final molecular assembly.Funding for open access charge: Universidad de Málaga / CBU