Showing papers on "Organic semiconductor published in 2008"

Organic semiconductors for solution-processable field-effect transistors (OFETs).

Abstract: The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing.

Exciton Diffusion Measurements in Poly(3‐hexylthiophene)

Abstract: The problem of making reliable measurements of exciton diffusion lengths in organic semiconductors is addressed. The exciton diffusion length is an extremely important quantity in the operation of organic solar cells. We focus on the polymer P3HT because of its widespread use in solar cells and are able to fit the exciton diffusion in a range of films with a single diffusion constant, showing that our approach is particularly robust.

Plasmon enhanced performance of organic solar cells using electrodeposited Ag nanoparticles

Abstract: To enhance solar harvesting in organic solar cells, uniform-sized metal nanoparticles of ∼13 nm were incorporated to the device via pulse-current electrodeposition, which is a kind of simple and quick solution process that can control the density and size of metal nanoparticles. By incorporating plasmonic Ag nanoparticles on surface modified transparent electrodes, overall power conversion efficiency was increased from 3.05% to 3.69%, mainly resulting from the improved photocurrent density as a result of enhanced absorption of the photoactive conjugate polymer due to the high electromagnetic field strength in the vicinity of the excited surface plasmons.

High-performance polymer heterojunction solar cells of a polysilafluorene derivative

Abstract: High-performance polymer heterojunction solar cells fabricated from an alternating copolymer of 2,7-silafluorene (SiF) and 4,7-di(2′-thienyl)-2,1,3-benzothiadiazole (DBT) (PSiF-DBT) as the electron donor blended with [6,6]-phenyl-C61-butyric acid methyl ester as the electron acceptor were investigated. A power-conversion efficiency up to 5.4% with an open-circuit voltage of 0.90V, a short-circuit current of 9.5mAcm−2, and a fill factor of 50.7% was achieved under the illumination of AM 1.5G from a calibrated solar simulator (800Wm−2). The field-effect transistors fabricated from PSiF-DBT showed a high hole mobility of ∼1×10−3cm2V−1s−1.

Contact-induced crystallinity for high-performance soluble acene-based transistors and circuits.

Abstract: The use of organic materials presents a tremendous opportunity to significantly impact the functionality and pervasiveness of large-area electronics. Commercialization of this technology requires reduction in manufacturing costs by exploiting inexpensive low-temperature deposition and patterning techniques, which typically lead to lower device performance. We report a low-cost approach to control the microstructure of solution-cast acene-based organic thin films through modification of interfacial chemistry. Chemically and selectively tailoring the source/drain contact interface is a novel route to initiating the crystallization of soluble organic semiconductors, leading to the growth on opposing contacts of crystalline films that extend into the transistor channel. This selective crystallization enables us to fabricate high-performance organic thin-film transistors and circuits, and to deterministically study the influence of the microstructure on the device characteristics. By connecting device fabrication to molecular design, we demonstrate that rapid film processing under ambient room conditions and high performance are not mutually exclusive.

Novel small molecules for organic field-effect transistors: towards processability and high performance

Abstract: The processing characteristics of organic semiconductors make them potentially useful for electronic applications where low-cost, large area coverage and structural flexibility are required. This critical review gives a general introduction about the current standing in the area of OFETs focusing on the new processable small molecules that have been recently reported for their use as organic semiconductors. A general description of the OFETs device operation and the transport mechanisms that dominate organic semiconductors is provided, followed by an overview of the strategies and materials employed to fabricate p-type, n-type and ambipolar OFETs. Some new tendencies and applications that are currently being developed employing OFETs are also described, such as the preparation of electronic paper, sensors or light emitting transistors (85 references).

Self-Organization of Ink-jet-Printed Triisopropylsilylethynyl Pentacene via Evaporation-Induced Flows in a Drying Droplet†

Abstract: We have demonstrated the influence of evaporation-induced flow in a single droplet on the crystalline microstructure and film morphology of an ink-jet-printed organic semiconductor, 6,13-bis((triisopropylsilylethynyl) pentacene (TIPS_PEN), by varying the composition of the solvent mixture. The ringlike deposits induced by outward convective flow in the droplets have a randomly oriented crystalline structure. The addition of dichlorobenzene as an evaporation control agent results in a homogeneous film morphology due to slow evaporation, but the molecular orientation of the film is undesirable in that it is similar to that of the ring-deposited films. However, self-aligned TIPS_PEN crystals with highly ordered crystalline structures were successfully produced when dodecane was added. Dodecane has a high boiling point and a low surface tension, and its addition to the solvent results in a recirculation flow in the droplets that is induced by a Marangoni flow (surface-tension-driven flow), which arises during the drying processes in the direction opposite to the convective flow. The field-effect transistors fabricated with these self-aligned crystals via ink-jet printing exhibit significantly improved performance with an average effective field-effect mobility of 0.12 cm2 V–1 s–1. These results demonstrate that with the choice of appropriate solvent ink-jet printing is an excellent method for the production of organic semiconductor films with uniform morphology and desired molecular orientation for the direct-write fabrication of high-performance organic electronics.

Room-temperature spintronic effects in Alq3-based hybrid devices

Abstract: We report on efficient spin polarized injection and transport in long (102 nm) channels of Alq3 organic semiconductor. We employ vertical spin valve devices with a direct interface between the bottom manganite electrode and Alq3, while the top-electrode geometry consists of an insulating tunnel barrier placed between the “soft” organic semiconductor and the top Co electrode. This solution reduces the ubiquitous problem of the so-called ill-defined layer caused by metal penetration, which extends into the organic layer up to distances of about 50–100 nm and prevents the realization of devices with well-defined geometry. For our devices the thickness is defined with an accuracy of about 2.5 nm, which is near the Alq3 molecular size. We demonstrate efficient spin injection at both interfaces in devices with 100- and 200-nm-thick channels. We solve one of the most controversial problems of organic spintronics: the temperature limitations for spin transport in Alq3-based devices. We clarify this issue by achieving room-temperature spin valve operation through the improvement of spin injection properties of both ferromagnetic/Alq3 interfaces. In addition, we discuss the nature of the inverse sign of the spin valve effect in such devices proposing a mechanism for spin transport.

Thin-Film Morphology Control in Naphthalene-Diimide-Based Semiconductors: High Mobility n-Type Semiconductor for Organic Thin-Film Transistors

Abstract: In organic thin film transistors (OTFT), the morphology and microstructure of an organic thin film has a strong impact on the charge carrier mobility and device characteristics. To have well-defined and predictable thin film morphology, it is necessary to adapt the basic structure of semiconducting molecules in a way that results in an optimum crystalline packing motif. Here we introduce a new molecular design feature for organic semiconductors that provides the optimized crystalline packing and thin film morphology that is essential for efficient charge-carrier transport. Thus, cyclohexyl end groups in naphthalene diimide assist in directing intermolecular stacking leading to a dramatic improvement in field effect mobility. Accordingly, OTFT devices prepared with vapor deposited N,N′-bis(cyclohexyl) naphthalene-1,4,5,8-bis(dicarboximide) (1) regularly exhibit field effect mobility near 6 cm2/(V s), which is one of the highest carrier mobilities reported for either n- or p-type organic semiconducting thin...

Photocurrent generation in nanostructured organic solar cells.

Abstract: Photocurrent generation in nanostructured organic solar cells is simulated using a dynamical Monte Carlo model that includes the generation and transport properties of both excitons and free charges. Incorporating both optical and electrical properties, we study the influence of the heterojunction nanostructure (e.g., planar vs bulk junctions) on donor-acceptor organic solar cell efficiencies based on the archetype materials copper phthalocyanine (CuPc) and C(60). Structures considered are planar and planar-mixed heterojunctions, homogeneous and phase-separated donor-acceptor (DA) mixtures, idealized structures composed of DA pillars, and nanocrystalline DA networks. The thickness dependence of absorption, exciton diffusion, and carrier collection efficiencies is studied for different morphologies, yielding results similar to those experimentally observed. The influences of charge mobility and exciton diffusion length are studied, and optimal device thicknesses are proposed for various structures. Simulations show that, with currently available materials, nanocrystalline network solar cells optimize both exciton diffusion and carrier collection, thus providing for highly efficient solar energy conversion. Estimations of achievable energy conversion efficiencies are made for the various nanostructures based on current simulations used in conjunction with experimentally obtained fill factors and open-circuit voltages for conventional small molecular weight materials combinations.

Influences of Crystal Structures and Molecular Sizes on the Charge Mobility of Organic Semiconductors: Oligothiophenes

Abstract: Both crystal packing and molecular size have strong influences on the charge mobility for organic semiconductors. The crystal structures for oligothiophene (nT) can be roughly classified into two types: the Z = 2 (two molecules in one unit cell) or high temperature (HT) phase and the Z = 4 or low temperature (LT) phase. Through first-principles calculations within the Marcus electron transfer theory coupled with random walk simulation for room temperature charge diffusion constants, we found that the hole mobility of the HT phase is about 3–4 times larger than that of the LT phase because the molecular packing in the HT phase favors the hole transfer (i.e., the frontier orbital wave function phases of the dimer are constructive, which tends to maximize the overlap), while for the LT phase, the molecules are packed in a position that reduces the intermolecular orbital overlap due to phase cancellation. As the molecular size increases from 2T to 8T, the hole mobility tends to increase because the reorganiza...

Expedient vapor probing of organic amines using fluorescent nanofibers fabricated from an n-type organic semiconductor.

Abstract: A new type of fluorescence sensory material with high sensitivity, selectivity, and photostability has been developed for vapor probing of organic amines. The sensory material is primarily based on well-defined nanofibers fabricated from an n-type organic semiconductor molecule, N-(1-hexylheptyl)perylene-3,4,9,10-tetracarboxyl-3,4-anhydride-9,10-imide. Upon deposition onto a substrate, the entangled nanofibers form a meshlike, highly porous film, which enables expedient diffusion of gaseous analyte molecules within the film matrix, leading to milliseconds response for the vapor sensing.

Light extraction and optical loss mechanisms in organic light-emitting diodes: Influence of the emitter quantum efficiency

Abstract: The internal quantum efficiency of organic light-emitting diodes (OLEDs) can reach values close to 100% if phosphorescent emitters to harvest triplet excitons are used; however, the fraction of light that is actually leaving the device is considerably less. Loss mechanisms are, for example, waveguiding in the organic layers and the substrate as well as the excitation of surface plasmon polaritons at metallic electrodes. Additionally, absorption in the organic layers and the electrodes can play a role. In this work we use numerical simulations to identify and quantify different loss mechanisms. Changing simulation parameters, for example, the distance of the emitter material to the cathode or thicknesses of the various layers, enables us to study their influence on the fraction of light leaving the OLED. An important parameter in these simulations and for the actual device is the radiative quantum efficiency q, which is defined as the efficiency of radiative exciton decay in an unbounded space filled by th...

Polarity Effects of Polymer Gate Electrets on Non‐Volatile Organic Field‐Effect Transistor Memory

Abstract: These func-tionalities arise from field-effect modulation by the chargesstored in chargeable polymer gate dielectrics, referred to aspolymer electrets.An electret is a piece of dielectric material that exhibits aquasi-permanent electrical charges or dipolar polarization,including ferro-, piezo-, and pyro-electric polymers.

Tuning of Ag work functions by self-assembled monolayers of aromatic thiols for an efficient hole injection for solution processed triisopropylsilylethynyl pentacene organic thin film transistors

Abstract: We demonstrate tuning of hole injection barriers in bottom contact triisopropylsilylethynyl pentacene (TIPS-pentacene) organic thin film transistors (OTFTs) by forming the self-assembled monolayers (SAMs) of thiophenol, 4-fluorothiophenol, or pentafluorothiophenol on the pristine Ag electrode. The work functions of SAM-treated Ag electrodes are measured by Kelvin probe method. The TIPS-pentacene OTFT devices were fabricated by a drop-cast method with a micropipette like an inkjet printing. The OTFTs with pentafluorothiophenol-Ag electrodes as source and drain exhibit carrier mobility of 0.17cm2∕Vs and on/off current ratio of 105 because of almost no hole injection barrier to TIPS pentacenes. The SAM-treated Ag electrodes are robust over repeated electrical scans of 100cycles.

Pentacene-based organic field-effect transistors

Abstract: Organic field-effect transistors (FETs) have attracted considerable attention because of their potential for realizing large-area, mechanically flexible, lightweight and low-cost devices. Pentacene, which is a promising material for organic FETs, has been intensely studied. This article reviews the basic properties of pentacene films and crystals, and the characteristics of pentacene FETs fabricated under various conditions, including our recent achievement of low-voltage operating high-mobility FETs. The basic properties include the crystal polymorph, the band structure and the effective mass. These data have been used for discussion of carrier transport and mobility in pentacene films. The characteristics of pentacene FETs generally depend on the conditions of the pentacene film and the gate-dielectric surface. The dependences are summarized in the article. In addition, liquid-crystal displays and organic light-emitting device arrays using pentacene FETs are reviewed as applications of organic FETs, and complementary metal–oxide–semiconductor circuits using our low-voltage operating FETs are also shown.

Transparent and conductive electrodes based on unpatterned, thin metal films

Abstract: Transparent electrodes composed of ultrathin, unpatterned metal films are investigated in planar heterojunction (PHJ) and bulk heterojunction organic photovoltaic (OPV) cells. Optimal electrode composition and thickness are deduced from electrical and optical models and experiments, enabling a PHJ-OPV cell to be realized using a silver anode, achieving power conversion efficiency parity with an analogous cell that uses an indium tin oxide anode. Beneficial aspects of smooth, unpatterned metal films as transparent electrodes in OPV cells are also discussed in the text.

Solution-Processed Bulk-Heterojunction Solar Cells Based on Monodisperse Dendritic Oligothiophenes†

Abstract: A novel family of soluble conjugated dendritic oligothiophenes (DOTs) as monodisperse 3D macromolecular architectures was characterized with respect to optical and redox properties in solution and in solid films. Band gaps of 2.5-2.2 eV, typical for organic semiconductors, were determined as well as HOMO/LUMO energy levels ideal for efficient electron transfer to acceptors such as [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) identifying them as suitable materials for solar cell applications. Solution-processed bulk-heterojunction solar cells using DOTs as electron donor and PCBM as acceptor were prepared and investigated. High open-circuit voltages V oc of 1.0 V and power-conversion efficiencies up to 1.72% were obtained for the DOT-based devices. The higher generations DOTs provide the highest efficiencies. Based on the monodispersity of the DOTs, an analysis of the molar ratio between donor and acceptor in the blended film was possible leading to an optimal value of five to six thiophene units per PCBM.

An Effective Friedel−Crafts Postfunctionalization of Poly(N-vinylcarbazole) to Tune Carrier Transportation of Supramolecular Organic Semiconductors Based on π-Stacked Polymers for Nonvolatile Flash Memory Cell

Abstract: Poly(N-vinylcarbazole) (PVK) and its derivatives are π-stacked polymers of the most important supramolecular organic semiconductors (SOSs), in which semiconducting features are originated from intra-supramolecular interactions. An effective Friedel−Crafts method has been developed to postfunctionalize PVK to a PVK−PF SOS and to tune the fundamental electronic structures and transporting properties of the resulting SOS. Stable nonvolatile flash memory effect from the SOS has been demonstrated in an ITO/PVK−PF/metal sandwich device. The device exhibited an ON/OFF current ratio up to 104, and writing/erasing voltages around +2.2/−2.0 V, respectively. The unique electrical bistability can be attributed to the ordering alignment effect induced by electric field and the hindrance effect arisen from bulky moieties. Thus, PVK-containing complicated 9,9-diarylfluorenes (CDAFs) are promising materials for information storage applications.

Energy levels at interfaces between metals and conjugated organic molecules

Abstract: The fundamental physical and chemical phenomena that can occur at interfaces between conjugated organic molecules and metal surfaces are discussed. The adsorption strength of molecular monolayers on metals covers a wide range from the weak physisorption regime to strong chemisorption, involving charge transfer and/or covalent bond formation. In many cases, molecular conformation changes can be observed, which directly impact the interface electronic structure and charge injection across the organic/metal contact. The energy level positions of organic multilayers are essentially determined by the monolayer/metal interaction, and 'flat-band' conditions prevail for thicker layers of pure organic molecules. Consequently, thermodynamic equilibrium across organic semiconductor films may not always be established.

Micrometer‐ and Nanometer‐Sized Organic Single‐Crystalline Transistors

Abstract: The use of micrometer and nanometer-sized organic single crystals to fabricate devices can retain all the advantages of single crystals, avoid the difficulties of growing large crystals, and provide a way to characterize organic semiconductors more efficiently. Moreover, the effective use of such "small" crystals will be beneficial to nanoelectronics. Here we review the recent progress of organic single-crystalline transistors based on micro-/nanometer-sized structures, namely fabrication methods and related technical issues, device properties, and current challenges.

Effects of arylene diimide thin film growth conditions on n-channel OFET performance

Abstract: A series of eight perylene diimide (PDI)- and naphthalene diimide (NDI)-based organic semiconductors was used to fabricate organic field-effect transistors (OFETs) on bare SiO2 substrates, with the substrate temperature during film deposition (Td) varied from 70–130 °C. For the N,N′-n-octyl materials that form highly ordered films, the mobility (µ) and current on-off ratio (Ion/Ioff) increase slightly from 70 to 90 °C, and remain relatively constant between 90 and 130 °C. Ion/Ioff and µ of dibromo-PDI-based OFETs decrease with increasing Td, while films of N,N′-1H,1H-perfluorobutyl dicyanoperylenediimide (PDI-FCN2) exhibit dramatic Ion/Ioff and µ enhancements with increasing Td. Increased OFET mobility can be correlated with higher levels of molecular ordering and minimization of film morphology surface irregularities. Additionally, the effects of SiO2 surface modification with trimethylsilyl and octadecyltrichlorosilyl monolayers, as well as with polystyrene, are investigated for N,N′-n-octyl dicyanoperylenediimide (PDI-8CN2) and PDI-FCN2 films deposited at Td = 130 °C. The SiO2 surface treatments have modest effects on PDI-8CN2 OFET mobilities, but modulate the mobility and morphology of PDI-FCN2 films substantially. Most importantly, the surface treatments result in substantially increased Vth and decreased Ioff values for the dicyanoperylenediimide films relative to those grown on SiO2, resulting in Vth > 0.0 V and Ion/Ioff ratios as high as 108. Enhancements in current modulation for these high-mobility, air-stable, and solution-processable n-type semiconductors, should prove useful in noise-margin enhancement and further improvements in organic electronics.

Electronic functionalization of the surface of organic semiconductors with self-assembled monolayers

Abstract: Self-assembled monolayers (SAMs) are widely used in a variety of emerging applications for surface modification of metals and oxides. Here, we demonstrate a new type of molecular self-assembly: the growth of organosilane SAMs at the surface of organic semiconductors. Remarkably, SAM growth results in a pronounced increase of the surface conductivity of organic materials, which can be very large for SAMs with a strong electron-withdrawing ability. For example, the conductivity induced by perfluorinated alkyl silanes in organic molecular crystals approaches 10(-5) S per square, two orders of magnitude greater than the maximum conductivity typically achieved in organic field-effect transistors. The observed large electronic effect opens new opportunities for nanoscale surface functionalization of organic semiconductors with molecular self-assembly. In particular, SAM-induced conductivity shows sensitivity to different molecular species present in the environment, which makes this system very attractive for chemical sensing applications.

Mechanism of charge transport in self-organizing organic materials

Abstract: Currently there is great interest in the use of organic materials as the active component in opto-electronic devices such as field-effect transistors, light-emitting diodes, solar cells and in nanoscale molecular electronics. Device performance is to a large extent determined by the mobility of charge carriers, which strongly depends on material morphology. Therefore, a fundamental understanding of the relation between the mechanism of charge transport and chemical composition and supramolecular organization of the active organic material is essential for improvement of device performance. Self-assembling materials are of specific interest, since they have the potential to form well defined structures in which molecular ordering facilitates efficient charge transport. This review gives an overview of theoretical models that can be used to describe the mobility of charge carriers, including band theory for structurally ordered materials, tight-binding models for weakly disordered systems and hopping models...

Field-effect-modulated Seebeck coefficient in organic semiconductors.

Abstract: Central to the operation of organic electronic and optoelectronic devices is the transport of charge and energy in the organic semiconductor, and to understand the nature and dynamics of charge carriers is at the focus of intense research efforts. As a basic transport property of solids, the Seebeck coefficient S provides deep insight as it is given by the entropy transported by thermally excited charge carriers and involves in the simplest case only electronic contributions where the transported entropy is determined by details of the band structure and scattering events. We have succeeded for the first time to measure the temperature- and carrier-density-dependent thermopower in single crystals and thin films of two prototypical organic semiconductors by a controlled modulation of the chemical potential in a field-effect geometry. Surprisingly, we find the Seebeck coefficient to be well within the range of the electronic contribution in conventional inorganic semiconductors, highlighting the similarity of transport mechanisms in organic and inorganic semiconductors. Charge and entropy transport is best described as band-like transport of quasiparticles that are subjected to scattering, with exponentially distributed in-gap trap states, and without further contributions to S. The nature of the charge transport in organic semiconductors is subject to intense research. A study on the thermal and charge transport of single-crystal thin-film polymers now shows close similarities between the transport properties of organic and inorganic semiconductors.