[Show abstract][Hide abstract] ABSTRACT: Despite their favorable electronic and structural properties, the synthetic development and incorporation of thiazole-based building blocks into n-type semiconductors has lagged behind that of other π-deficient building blocks. Since thiazole insertion into π-conjugated systems is synthetically more demanding, continuous research efforts are essential to underscore their properties in electron-transporting devices. Here, we report the design, synthesis, and characterization of a new series of thiazole–thiophene tetra- (1 and 2) and hexa-heteroaryl (3 and 4) co-oligomers, varied by core extension and regiochemistry, which are end-functionalized with electron-withdrawing perfluorohexyl substituents. These new semiconductors are found to exhibit excellent n-channel OFET transport with electron mobilities (μe) as high as 1.30 cm2/(V·s) (Ion/Ioff > 106) for films of 2 deposited at room temperature. In contrary to previous studies, we show here that 2,2′-bithiazole can be a very practical building block for high-performance n-channel semiconductors. Additionally, upon 2,2′- and 5,5′-bithiazole insertion into a sexithiophene backbone of well-known DFH-6T, significant charge transport improvements (from 0.001–0.021 cm2/(V·s) to 0.20–0.70 cm2/(V·s)) were observed for 3 and 4. Analysis of the thin-film morphological and microstructural characteristics, in combination with the physicochemical properties, explains the observed high mobilities for the present semiconductors. Finally, we demonstrate for the first time implementation of a thiazole semiconductor (2) into a trilayer light-emitting transistor (OLET) enabling green light emission. Our results show that thiazole is a promising building block for efficient electron transport in π-conjugated semiconductor thin-films, and it should be studied more in future optoelectronic applications.
Full-text · Article · Nov 2014 · Chemistry of Materials
[Show abstract][Hide abstract] ABSTRACT: In this work, we report on the fabrication and characterization of organic light-emitting transistors (OLETs) within an indium–tin-oxide (ITO)-free platform, using graphene-based transparent conductive electrodes in place of ITO as gate electrode. A direct comparison between twin bottom-gate/top-contacts OLETs, where a standard ITO layer is replaced with a film made of a few graphene layers, shows that comparable electrical characteristics can be obtained along with a clear improvement in the electroluminescence generation characteristics. Our experimental findings pave the way to the exploitation of graphene-based transparent conductive electrodes within this class of emerging devices on flexible substrates, further promoting the novel era of flexible organic electronics.
[Show abstract][Hide abstract] ABSTRACT: Herein is described a multidisciplinary approach to understand the performance limitations of small molecule organic light emitting transistors (OLETs) based on a layered architecture, an innovative architecture potentially competitive with the state of the art and more flexible for spectral emission control. The processes of charge injection and field-effect transport at metal/organic and organic/organic interfaces are analysed using microscopic and spectroscopic techniques in coordination. Atomic force microscopy and ultrasonic force microscopy are employed to characterize the interface morphology and the initial growth stages of organic films where charge transport actually occurs. X-ray diffraction and near edge X-ray dichroic absorption with linearly polarised light allow to determine the unit cell packing and the molecular orientation at the active organic interfaces, as well as the amount of non-ordered domains. Moreover, chemical reactivity at the interfaces are measured by X-ray photoelectron spectroscopy. It is found that a strong reaction occurs at the metal-organic interfaces, with molecular fragmentation. Additionally, the transport properties strongly depend on the nature of the materials forming the organic stack. Specifically, amorphous conjugated films as bottom layers can promote an increased molecular disorder in the upper active layer, with a concomitant deterioration of the conduction properties.
[Show abstract][Hide abstract] ABSTRACT: The relationships between the molecular structure, packing modalities, charge mobility and light emission in organic thin films is a highly debated and controversial issue, with both fundamental and technological implications in the field of organic optoelectronics. Thieno(bis)imide (TBI) based molecular semiconductors provide an interesting combination of good processability, tunable self-assembly, ambipolar charge transport and electroluminescence, and are therefore an ideal test base for fundamental studies on the structure-property correlation in multifunctional molecular systems. Herein, we introduce a new class of thieno(bis)imide quaterthiophenes having alkyl side chains of different shapes (linear, cyclic, branched) and lengths (C1-C8). We found that contrarily to what is generally observed in most molecular semiconductors, the length of the alkyl substituent does not affect the optical, self-assembly and charge transport properties of TBI materials. However, different electroluminescence powers are observed by increasing the alkyl side, this suggesting a potential tool for the selective modulation of TBI functionalities. A deep experimental and theoretical investigation on this new family of TBI materials is provided.
No preview · Article · May 2014 · Journal of Materials Chemistry
[Show abstract][Hide abstract] ABSTRACT: A novel method for mapping the charge density spatial distribution in organic field-effect transistors based on the electro-modulation of the photoluminescence is demonstrated. In field-effect transistors exciton quenching is dominated by exciton-charge carrier interaction so that it can be used to map the charge distribution in different operating conditions. From a quantitative analysis of the photoluminescence quenching, the thickness of the charge-carrier accumulation layer is derived. The injection of minority charge carriers in unipolar conditions is unexpectedly evidenced, which is not displayed by the electrical characteristics.
[Show abstract][Hide abstract] ABSTRACT: Organic light-emitting transistors (OLETs) are multifunctional optoelectronic devices that hold great promise for a variety of applications, including flat panel displays, integrated light sources for sensing and optical communication systems. The narrow illumination area within the device channel is considered intrinsic to the device architecture and is a severe technological drawback for all those applications where a controlled, wide and homogeneous emission area is required. Here it is shown that not only the position but also the extension of the emission area is voltage-tunable, and the entire channel of the transistor can be homogeneously illuminated. The modeling of the exciton distribution within the channel at the different bias conditions coupled to the modeling of the device emission profile highlights that excitons are spread through the entire channel width and across the bulk of the central emission layer of the p-channel/emitter/n-channel trilayer active heterostructure.
No preview · Article · Nov 2013 · Laser & Photonics Review
[Show abstract][Hide abstract] ABSTRACT: We performed constant voltage stress on oligothiophene-based p- and n-type organic thin-film-transistors, in the accumulation regime. The stress induced charge trapping, mobility degradation and defect generation. The specific kinetics depends not only on the applied bias value and polarity, but also on the semiconductor type. Stress on PMMA capacitors (without the semiconductor film) revealed that most of the degradation is largely originated by the interaction with the semiconductor layer, which enhances charge injection.
No preview · Article · Nov 2013 · Microelectronics Reliability
[Show abstract][Hide abstract] ABSTRACT: The synthesis of two new thieno(bis)imide (TBI, N) end functionalized oligothiophene semiconductors is reported. In particular, trimer (NT3N) and pentamer (NT5N) have been synthesized and characterized. Two different synthetic approaches for their preparation were tested and compared namely conventional Stille cross coupling and direct arylation reaction via C–H activation. Theoretical calculations, optical and electrochemical characterization allowed us to assess the role of the π-conjugation extent, i.e., of the oligomer size on the optoelectronic properties of these materials. In both TBI ended compounds, due to the strong localization of the LUMO orbital on the TBI unit, the LUMO energy is almost insensitive to the oligomer size, this being crucial for the fine-tailoring of the energy and the distribution of the frontier orbitals. Surprisingly, despite its short size and contrarily to comparable TBI-free analogues, NT3N shows electron charge transport with mobility up to μN = 10−4 cm2 V−1 s−1, while increasing the oligomer size to NT5N promotes ambipolar behavior and electroluminescence properties with mobility up to μN = 0.14 cm2 V−1 s−1 and to μP = 10−5 cm2 V−1 s−1.
No preview · Article · Nov 2013 · Organic Electronics
[Show abstract][Hide abstract] ABSTRACT: Despite the variety of functional properties of molecular materials, which make them of interest for a number of technologies, their tendency to form inhomogeneous aggregates in thin films and to self-organize in polymorphs are considered drawbacks for practical applications. Here, we report on the use of polymorphic molecular fluorescent thin films as time temperature integrators, a class of devices that monitor the thermal history of a product. The device is fabricated by patterning the fluorescent model compound thieno(bis)imide-oligothiophene. The fluorescence colour of the pattern changes as a consequence of an irreversible phase variation driven by temperature, and reveals the temperature at which the pattern was exposed. The experimental results are quantitatively analysed in the range 20-200°C and interpreted considering a polymorph recrystallization in the thin film. Noteworthy, the reported method is of general validity and can be extended to every compound featuring irreversible temperature-dependent change of fluorescence.
[Show abstract][Hide abstract] ABSTRACT: Organic molecular semiconductors are key components for a new generation of low cost, flexible, and large area electronic devices. In particular, ambipolar semiconductors endowed with electroluminescent properties have the potential to enable a photonic field-effect technology platform, whose key building blocks are the emerging organic light-emitting transistor (OLET) devices. To this aim, the design of innovative molecular configurations combining effective electrical and optical properties in the solid state is highly desirable. Here, we investigate the effect of the insertion of a thieno(bis)imide (TBI) moiety as end group in highly performing unipolar oligothiophene semiconductors on the packing, electrical, and optoelectronic properties of the resulting materials. We show that, regardless of the HOMO–LUMO energy, orbital distribution, and molecular packing pattern, a TBI end moiety switches unipolar and nonemissive oligothiophene semiconductors to ambipolar and electroluminescent materials. Remarkably, the newly developed materials enabled the fabrication of single layer molecular ambipolar OLETs with optical power comparable to that of the equivalent polymeric single layer devices.
No preview · Article · Feb 2013 · Chemistry of Materials
[Show abstract][Hide abstract] ABSTRACT: The synthesis and characterization of two thieno(bis)imide based n-type semiconductors with electron mobilities of up to 0.3 cm(2) V(-1) s(-1) are described. The relationships between the electronic features of the π-inner core and the functional properties of the new materials are also discussed.
Preview · Article · Nov 2012 · Chemical Communications
[Show abstract][Hide abstract] ABSTRACT: In this Article, we present a comprehensive study of organic field-effect transistors (OFETs) made of thin films of methyl, n-butyl, and n-hexyl end-substituted quaterthiophenes on a transparent substrate platform. This particular platform has been already used for organic light-emitting diodes (OLEDs) but rarely employed for OFETs. In perspective, this is a very promising route for the development of field-effect photonic applications such as organic light-emitting transistors (OLETs). A systematic characterization of the organic films has been made by means of atomic force microscopy (AFM) and X-ray diffraction (XRD) to correlate morphology, crystallinity and charge mobility to the alkyl chain length. In particular, a charge mobility value of 0.09 cm2/(V s) has been obtained in transparent OFETs with a large area channel for DH4T grown at room temperature. This mobility exceeds the one obtained on silicon-oxide substrates and is likely due to a more favorable interaction of the DH4T molecules with the PMMA layer employed as gate dielectric.
No preview · Article · Nov 2011 · The Journal of Physical Chemistry C
[Show abstract][Hide abstract] ABSTRACT: The design, synthesis and structure-property investigation of a new thienopyrrolyl dione substituted oligothiophene material showing reduced band gap energy, low lying LUMO energy level and ambipolar semiconducting behaviour is described.
No preview · Article · Sep 2011 · Chemical Communications
[Show abstract][Hide abstract] ABSTRACT: Interest in electronic properties of organic materials has been stimulated by emerging prospects of their application in electronics and photonics [1-4]. Among potential applications, one may envisage use of organic materials as active elements of molecular switches. According to a general definition, a switch is a mechanical, electrical, electronic, or optical device for opening or closing a circuit, or for diverting energy or charge from one part of a circuit to another. In this context, photochromic materials have been extensively studied.
[Show abstract][Hide abstract] ABSTRACT: We present the integration of a natural protein into electronic and optoelectronic devices by using silk fibroin as a thin film dielectric in an organic thin film field-effect transistor (OFET) ad an organic light emitting transistor device (OLET) structures. Both n- (perylene) and p-type (thiophene) silk-based OFETs are demonstrated. The measured electrical characteristics are in agreement with high-efficiency standard organic transistors, namely charge mobility of the order of 10(-2) cm(2)/Vs and on/off ratio of 10(4). The silk-based optolectronic element is an advanced unipolar n-type OLET that yields a light emission of 100nW.
[Show abstract][Hide abstract] ABSTRACT: In this paper, we present a study of the effects of the influence of the substrate platform on the properties of a three-layer vertical hetero-junction made of thin films of α, ω-diperfluorohexyl-4T (DHF4T), a blend of tris(8-hydroxyquinoline)aluminium (Alq3) and 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) and α, ω-dihexyl-quaterthiophene (DH4T). The hetero-junction represents the active component of an organic light-emitting transistor (OLET). The substrate platforms investigated in this study are glass/indium-tin-oxide/poly(methyl-methacrylate) (PMMA) and Si++/silicon oxide (SiO2)/PMMA. The first platform is almost completely transparent to light and therefore is very promising for use in OLET applications. The second one has been chosen for comparison as it employs standard microelectronic materials, i.e. Si++/SiO2. We show how different gate materials and structure can affect the relevant field-effect electrical characteristics, such as the charge mobility and threshold voltage. By means of an atomic force microscopy analysis, a systematic study has been made in order to correlate the morphology of the active layers with the electrical properties of the devices.
Full-text · Article · May 2011 · Journal of Physics D Applied Physics
[Show abstract][Hide abstract] ABSTRACT: Increasing interest in multistable photochromic systems observed in recent years has been due to emerging applications in organic electronics and photonics . There are many examples of using photochromic materials as admixtures to organic semiconductors in electronic devices . In the present communication we describe an organic field effect transistor (OFET) in which photochromic spiropyran was admixed to the gate insulator (PMMA) and not to semiconductor (in this study we used n-type perylene derivative P13).
The modulation of the source-drain currents measured in studied OFETs was due to reversible photochemical reaction of spiropyran, the photoswitching ratio depending on gate voltage. The phenomenon was attributed to changes in dipole moment of photochromic molecules during the reaction, its mechanism being related to a contribution of the photochromic dipoles on the semiconductor-insulator interface and in the bulk of the insulator .
This work was supported by the European Commission through the Human Potential Programme (Marie-Curie RTN BIMORE, Grant No. MRTN-CT-2006-035859) and, in part, by the Wroclaw University of Technology.
 B.L. Feringa (Ed.), “Molecular Switches” Wiley-VCH, Weinheim 2001.
 P. Lutsyk, J. Sworakowski, K. Janus, S. Nešpůrek, A. Kochalska, Mol. Cryst. Liq. Cryst. 522, 211 (2010).
 P. Lutsyk, K. Janus, J. Sworakowski, G. Generali, R. Capelli, M. Muccini, J. Phys. Chem. C accepted (2011).
[Show abstract][Hide abstract] ABSTRACT: Astroglial cell survival and ion channel activity are relevant molecular targets for the mechanistic study of neural cell interactions with biomaterials and/or electronic interfaces. Astrogliosis is the most typical reaction to in vivo brain implants and needs to be avoided by developing biomaterials that preserve astroglial cell physiological function. This cellular phenomenon is characterized by a proliferative state and altered expression of astroglial potassium (K(+)) channels. Silk is a natural polymer with potential for new biomedical applications due to its ability to support in vitro growth and differentiation of many cell types. We report on silk interactions with cultured neocortical astroglial cells. Astrocytes survival is similar when plated on silk-coated glass and on poly-D-lysine (PDL), a well known polyionic substrate used to promote astroglial cell adhesion to glass surfaces. Comparative analyses of whole-cell patch-clamp experiments reveal that silk- and PDL-coated cells display depolarized resting membrane potentials (-40 mV), very high input resistance, and low specific conductance, with values similar to those of undifferentiated glial cells. Analysis of K(+) channel conductance reveals that silk-astrocytes express large outwardly delayed rectifying K(+) current (K(DR)). The magnitude of K(DR) in PDL- and silk-coated astrocytes is similar, indicating that silk does not alter the resting K(+) current. We also demonstrate that guanosine- (GUO) embedded silk enables the direct modulation of astroglial K(+) conductance in vitro. Astrocytes plated on GUO-embedded silk are more hyperpolarized and express inward rectifying K(+) conductance (K(ir)). The K(+) inward current increases and this is paralleled by upregulation and membrane polarization of K(ir)4.1 protein signal. Collectively these results indicate that silk is a suitable biomaterial platform for the in vitro studies of astroglial ion channel responses and related physiology.
[Show abstract][Hide abstract] ABSTRACT: Organic field-effect transistors (OFETs) are alternative emerging device structures for efficient light generation, that could provide a novel architecture to address open issues like exciton-contact and exciton-charge quenching, that still limit the OLEDs efficiency and brightness.Recently, it has been introduced by our research group the model of a tri-layer organic heterostructure implemented in a field-effect configuration, that allows preventing at one time the exciton-metal as well as the exciton-charge quenching in an organic electroluminescence generating device. The device active region is formed by a central optical layer sandwiched between an electron and a hole field-effect conducting film. In order to understand the complex phenomena that happens at the interfaces, with the target to fabricate the most balanced ambipolar structure with high morphological compatibility and high mobility in a vertical heterojunction geometry, we made a preliminary study of a single layer and bi-layer OFET structure composed by α,ω-dihexylquaterthiophene (DH4T) and α,ω-diperfluoroquaterthiophene (DHF4T). By means of this study we showed a new highly balanced ambipolar OFET made of these materials, a first step toward their implementation in a more complex structure as the tri-layer is.
No preview · Article · Sep 2010 · Microelectronics Reliability