A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm(2) V(-1) s(-1) and 0.56 cm(2) V(-1) s(-1), respectively, are achieved for PDPP-FBF.     

Development of a new conjugated polymer containing dialkoxynaphthalene for efficient polymer solar cells and organic thin film transistors

A new semiconducting polymer, poly((5,5‐E‐α‐((2‐thienyl)methylene)‐2‐thiopheneacetonitrile)‐alt‐2,6‐[(1,5‐didecyloxy)naphthalene])) (PBTADN), an alternating copolymer of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile and didecyloxy naphthalene, is synthesized and used as an active material for organic thin film transistors (OTFTs) and organic solar cells. The incorporation of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile as an electron deficient group and didecyloxy naphthalene as an electron rich group resulted in a relatively low bandgap, high charge carrier mobility, and finally good photovoltaic performances of PBTADN solar cells. Because of the excellent miscibility of PBTADN and PC₇₁BM, as confirmed by Grazing Incident X‐ray Scattering (GIXS) measurements and Transmission Electron Microscopy (TEM), homogeneous film morphology was achieved. The maximum power conversion efficiency of the PBTADN:PC₇₁BM solar cell reached 2.9% with a V_oc of 0.88 V, a short circuit current density (J_sc) of 5.6 mA/cm², and a fill factor of 59.1%. The solution processed thin film transistor with PBTADN revealed a highest saturation mobility of 0.025 cm²/Vs with an on/off ratio of 10⁴. The molecular weight dependence of the morphology, charge carrier mobility, and finally the photovoltaic performances were also studied and it was found that high molecular weight PBTADN has better self assembly characteristics, showing enhanced performance. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Bistability in doped organic thin film transistors

Organic thin film transitors (TFTs) with the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid), PEDOT:PSS, as the active layer and cross-linked, layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) multilayers as the gate dielectric layer were investigated. A combination of spectroscopic data and device performance characteristics was used to study the behavior of these TFT devices under a variety of controlled environmental test conditions. It was shown that depletion and recovery of the device can be induced to occur by a means that is consistent with the electrochemical oxidation and reduction of water contained in the film. In addition to acting as a reactant, moisture also acts as a plasticizer to control the mobility of other species contained in the film and thereby permits bistable operation of these devices. Raman spectroscopy was used to show that the observed device switching behavior is due to a change in the PEDOT doping level.     

Diketopyrrolopyrrole‐based conjugated polymers and small molecules for organic ambipolar transistors and solar cells

The present highlight discusses major work in the synthesis of low bandgap diketopyrrolopyrrole ( DPP )‐based polymers with donor–acceptor–donor ( D–A–D ) approach and their application in organic electronics. It examines the past and recent significant advances which have led to development of low bandgap DPP ‐based materials with phenyl and thiophene as donors. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4241–4260     

Annealing-free high-mobility diketopyrrolopyrrole-quaterthiophene copolymer for solution-processed organic thin film transistors

A donor-acceptor polymer semiconductor, PDQT, comprising diketopyrrolopyrrole (DPP) and β-unsubstituted quaterthiophene (QT) for organic thin film transistors (OTFTs) is reported. This polymer forms ordered layer-by-layer lamellar packing with an edge-on orientation in thin films even without thermal annealing. The strong intermolecular interactions arising from the fused aromatic DPP moiety and the DPP-QT donor-acceptor interaction facilitate the spontaneous self-assembly of the polymer chains into close proximity and form a large π-π overlap, which are favorable for intermolecular charge hopping. The well-interconnected crystalline grains form efficient intergranular charge transport pathways. The desirable chemical, electronic, and morphological structures of PDQT bring about high hole mobility of up to 0.97 cm(2)/(V·s) in OTFTs with polymer thin films annealed at a mild temperature of 100 °C and similarly high mobility of 0.89 cm(2)/(V·s) for polymer thin films even without thermal annealing.     

Molecular design of n-type organic semiconductors for high-performance thin film transistors

This digest aims to provide organic chemists with an overview of recent progress on n-type organic semiconductors for application in organic thin film transistors (OTFTs) with an emphasis on molecular design. Herein, we survey n-type organic semiconductors with field effect mobility of 1 cm²/Vs or higher in OTFTs after a brief introduction to the structure and operation of OTFTs and discussion of two key factors (frontier molecular orbitals and molecular packing) of organic semiconductors. On the basis of this survey, we finally reach conclusions on the current status of n-type organic semiconductors for OTFTs and provide an outlook for molecular design.     

An isoindigo-bithiazole-based acceptor-acceptor copolymer for balanced ambipolar organic thin-film transistors

Balanced carrier transport is observed in acceptor-acceptor (A-A′) type polymer for ambipolar organic thin-film transistors B (OTFTs). It is found that the incorporation of two electron-accepting moieties (BTz and IIG) into a polymer main chain to form A-A′ polymer PIIG-BTz could lower highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels and facilitate good molecular stacking of the polymer. Ambipolar transistor behaviour for PIIG-BTz, with the balanced hole and electron mobilities of 0.030 and 0.022 cm2 V-1 s-1 was observed in OTFT devices, respectively. The study in this work reveals that the utilization of acceptor-acceptor (A-A′) structure in polymer main chain can be a feasible strategy to develop ambipolar polymer semiconductors.     

Acceptor-donor-acceptor conjugated oligomers based on diketopyrrolopyrrole and thienoacenes with four,five and six rings for organic thin-film transistors

Three acceptor-donor-acceptor(A-D-A) conjugated oligomers, i.e., O1, O2 and O3, have been synthesized using diketopyrrolopyrrole(DPP) as an electron-acceptor unit, and naphtho[1,2-b:5,6-b']dithiophene(NDT), anthra[1,2-b:5,6-b']dithiophene(ADT) or dithieno[3,2-b:3',2'-b']naphtho[1,2-b:5,6-b']dithiophene(DTNDT) as electron-donor unit. These oligomers exhibit identical highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) energy levels, which were ca.-5.1 and-3.3 eV, respectively. Upon thermal annealing, all three oligomers formed thin films with ordered microstructures, and their organic thin film transistors(OTFTs) exhibited p-type transport behavior. The mobility was increased with an extension of the size of D-units. O3 showed the best OTFT performance with the mobility of up to 0.20 cm~2·V~(-1)·s~(-1). The film quality of O3 was improved by adding 1 wt% poly(methylmethacrylate)(PMMA). In consequence, the mobility of the O3-based devices was further enhanced to 0.30 cm~2·V~(-1)·s~(-1).     

Ambipolar, high performance, acene-based organic thin film transistors

We present a high performance, ambipolar organic field-effect transistor composed of a single material. Ambipolar molecules are rare, and they can enable low-power complementary-like circuits. This low band gap, asymmetric linear acene contains electron-withdrawing fluorine atoms, which lower the molecular orbital energies, allowing the injection of electrons. While hole and electron mobilities of up to 0.071 and 0.37 cm2/V.s, respectively, are reported on devices measured in nitrogen, hole mobilities of up to 0.12 cm2/V.s were found in ambient, with electron transport quenched. These devices were fabricated on octadecyltrimethoxysilane-treated surfaces at a substrate temperature of 60 degrees C.     

Structure and properties of small molecule-polymer blend semiconductors for organic thin film transistors

A comprehensive structural and electrical characterization of solution-processed blend films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconductor and poly(alpha-methylstyrene) (PalphaMS) insulator was performed to understand and optimize the blend semiconductor films, which are very attractive as the active layer in solution-processed organic thin-film transistors (OTFTs). Our study, based on careful measurements of specular neutron reflectivity and grazing-incidence X-ray diffraction, showed that the blends with a low molecular-mass PalphaMS exhibited a strong segregation of TIPS-pentacene only at the air interface, but surprisingly the blends with a high molecular-mass PalphaMS showed a strong segregation of TIPS-pentacene at both air and bottom substrate interfaces with high crystallinity and desired orientation. This finding led to the preparation of a TIPS-pentacene/PalphaMS blend active layer with superior performance characteristics (field-effect mobility, on/off ratio, and threshold voltage) over those of neat TIPS-pentacene, as well as the solution-processability of technologically attractive bottom-gate/bottom-contact OTFT devices.     

Toward n-channel organic thin film transistors based on a distyryl-bithiophene derivatives

Solution and solid-state properties of two new perfluoroalkyl end-substituted analogues of distyryl-bithiophene (CF₃-DS2T and diCF₃-DS2T) are presented. Vacuum deposited thin films were investigated by atomic force microscopy, X-ray diffraction, and implemented as active layers into organic thin film transistors. While physicochemical measurements in solution suggest a preferential hole injection and transport inside CF₃-DS2T and diCF₃-DS2T films, electrical measurements performed under high vacuum show that CF₃-DS2T behaves as n-type semiconductor while no charge transport was measured in diCF₃-DS2T. The results highlighted the importance of substituents on conjugated backbone and on the resulting fine ordering in solid state to control the charge transport.     

Thiadiazoloquinoxaline-acetylene containing polymers as semiconductors in ambipolar field effect transistors

Two conjugated copolymers, PPTQT and PTTQT, were developed based on thiadiazoloquinoxalines connected via ethynylene π-spacer to thiophene units. PPTQT showed maximum hole and electron mobility of 0.028 and 0.042 cm(2)/V s, respectively, being the first example of an ambipolar semiconducting material bearing triple bonds in the polymer backbone.     

Synthesis and characterization of poly(benzodithiophene) derivative for organic thin film transistors

Poly{2,6‐bis(3‐dodecylthiophen‐2‐yl) benzo[1,2‐b;4,5‐b′]dithiophene} (PTBT) was synthesized, via oxidative polymerization by oxidative agent (FeCl₃). The mole ratio of FeCl₃ and monomer (3.5:1), and keeping low temperature during the dropping of diluted catalyst were very important for the polymerization without crosslinking. The PTBT was confirmed by ¹H NMR, FTIR spectra, and elemental analysis. The PTBT has very good solubility in organic solvents such as chloroform, tetrahydrofuran, etc, and good thermal stability with T_g of 164 °C. The PTBT shows UV‐optical absorption at 406 nm and photoluminescence (PL) spectroscopy at 504 nm in a film. The highest occupied molecular orbital (HOMO) energy of the polymer is ?5.71 eV by measuring cyclic voltammetry (CV). A solution‐processed polymer thin film transistor device shows a mobility of 3 × 10^?5 – 8 × 10^?5 cm² V^?1 s^?1, and an on/off current ratio of 10⁴. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5277–5284, 2007     

Thienopyrrolyl dione end-capped oligothiophene ambipolar semiconductors for thin film- and light emitting transistors

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.     

High-performance,solution-processed organic thin film transistors from a novel pentacene precursor

The Lewis acid-catalyzed Diels-Alder reaction of the organic semiconductor pentacene with N-sulfinylacetamide yields a soluble adduct. Spin-coated thin films of this adduct undergo solid-phase conversion to form thin films of pentacene at moderate temperatures. Organic thin film transistors fabricated by spin-coating this adduct, followed by thermal conversion to pentacene, exhibit the highest mobility reported to date for a solution-processed organic semiconductor.     

Control of polymorphism in solution-processed organic thin film transistors by self-assembled monolayers

Polymorphism of organic semiconductor films is of key importance for the performance of organic thin film transistors(OTFTs).Herein, we demonstrate that the polymorphism of solution-processed organic semiconductors in thin film transistors can be controlled by finely tuning the surface nanostructures of substrates with self-assembled monolayers(SAMs). It is found that the SAMs of 12-cyclohexyldodecylphosphonic acid(CDPA) and 12-phenyldodecylphosphonic acid(Ph DPA) induce different polymorphs in the dip-coated films of 2-dodecyl[1]benzothieno[3,2-b][1]benzothiophene(BTBT-C12). The film of BTBT-C12 on CDPA exhibits field effect mobility as high as 28.1 cm~2 V~(-1) s~(-1) for holes, which is higher than that of BTBT-C12 on Ph DPA by three times. The high mobility of BTBT-C12 on CDPA is attributable to the highly oriented films of BTBT-C12 with a reduced in-plane lattice and high molecular alignment.     

High performance semiconducting polymers containing bis(bithiophenyl dithienothiophene)‐based repeating groups for organic thin film transistors

New dithienothiophene‐containing conjugated polymers, such as poly(2,6‐bis(2‐thiophenyl‐3‐dodecylthiophene‐2‐yl)dithieno[3,2‐b;2′,3′‐d]thiophene, 4 and poly(2,6‐bis (2‐thiophenyl‐4‐dodecylthiophene‐2‐yl)dithieno[3,2‐b;2′,3′‐d]thiophene, 8 have been successfully synthesized via Stille coupling reactions using dodecyl‐substituted thiophene‐based monomers, bistributyltin dithienothiophene, and bistributyltin bithiophene; these polymers have been fully characterized. The main difference between the two polymers is the substitution position of the dodecyl side chains in the repeating group. Grazing‐incidence X‐ray diffraction (GI‐XRD) gave clear evidence of edge‐on orientation of polycrystallites to the substrate. The semiconducting properties of the two polymers have been evaluated in organic thin film transistors (OTFTs). The two conjugated polymers 4 and 8 exhibit fairly high hole carrier mobilities as high as μ_ave = 0.05 cm²/Vs (I_ON/OFF = 3.42 × 10⁴) and μ_ave = 0.01 cm²/Vs, (I_ON/OFF = 1.3 × 10⁵), respectively, after thermal annealing process. The solvent annealed films underwent reorganization of the molecules to induce higher crystallinity. Well‐defined atomic force microscopy (AFM) topography supported a significant improvement in TFT device performance. The hole carrier mobilities of the solvent annealed films are comparable to those obtained for a thermally annealed sample, and were one‐order higher than those obtained with a pristine sample. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A new imidazolylquinoline for organic thin film transistor

A new active electronic material, 2-(naphtho[3,4]imidazol-2-yl)quinoline (NIQ), 1, has been synthesized and fully characterized. This compound exhibits field-effect carrier mobility and behaves as a p-type semiconductor (μ_FET = 0.148 cm²/V s at V_DS = 10 V). NIQ and its related imidazolylquinoline compounds may have possible applications as active materials in organic thin film transistors.     

Alpha,omega-distyryl oligothiophenes: high mobility semiconductors for environmentally stable organic thin film transistors

Critical to the development of organic electronics is the design and synthesis of new organic semiconductors with improved electrical performance and enhanced environmental stability. We present in this communication the synthesis of a series of simple oligothiophene derivatives that bear the styryl unit as terminal substituent. Thin film field-effect transistors incorporating these compounds show high electrical performance, such as mobilities as high as 0.1 cm2/Vs, along with exceptional stability under ambient conditions. Especially, the longer oligomer, DS-4T, containing the quaterthiophene core gives rise to devices that show no decrease in performance after more than 17 months of storage and under continuous operation. Such stability features are unprecedented in the oligothiophene series.     

Synthesis of polymer dielectric layers for organic thin film transistors via surface-initiated ring-opening metathesis polymerization

The use of surface-initiated ring-opening metathesis polymerization (SI-ROMP) for producing polymer dielectric layers is reported. Surface tethering of the catalyst to Au or Si/SiO2 surfaces is accomplished via self-assembled monolayers of thiols or silanes containing reactive olefins. Subsequent SI-ROMP of norbornene can be conducted under mild conditions. Pentacene semiconducting layers and gold drain/source electrodes are deposited over these polymer dielectric films. The resulting field effect transistors display promising device characteristics, demonstrating for the first time that SI-ROMP can be used in the construction of organic thin-film electronic devices.