Synergistic effect of polymer and oligomer blends for solution-processable organic thin-film transistors

The thin-film morphologies and thin-film transistor (TFT) characteristics of a series of binary blends of poly(9,9′-dioctylfluorene-alt-bithiophene) (F8T2) and α,ω-dihexylquarterthiophene (DH4T) are reported. The blends of F8T2 and DH4T exhibit good solubility and produce TFT devices with better performances than F8T2 and DH4T devices. The 50% DH4T blend device was found to have a hole mobility of 0.011 cm ² V⁻¹ s⁻¹, which is four times higher than the mobility of the F8T2 device, with a high-on/off ratio of about 10⁵ and a low-off current of 17 pA. The polymer and oligomer domains are phase-separated with large domain size and arranged in characteristic molecular alignments. It was found that carrier transport in the blend systems is mainly controlled by the polymer component, and that the nature of the blended oligomer affects the OTFT performance of the blends.     

Enhancement of the field-effect mobility of poly(3-hexylthiophene)/functionalized carbon nanotube hybrid transistors

With the aim of enhancing the field-effect mobility of poly(3-hexylthiophene) (P3HT) field-effect transistors (FETs), we added functionalized multiwalled carbon nanotubes (CNTs) to the P3HT solution prior to film formation. The nanotubes were found to be homogeneously dispersed in the P3HT films because of their functional groups. We found that at the appropriate CNT concentration (up to 10 wt% CNT), the P3HT FETs have a high field-effect mobility of 0.04 cm² V⁻¹ s⁻¹, which is an improvement by a factor of more than 10. This remarkable increase in the field-effect mobility over that of the pristine P3HT film is due to the high conductivity of the CNTs which act as conducting bridges between the crystalline regions of the P3HT film, and the reduction in the hole-injection barrier due to the low work function of CNTs, which results in more efficient carrier injection.     

High mobility and low operation voltage organic field effect transistors by using polymer-gel dielectric and molecular doping

In this work, we present a method to increase the performance in solution processed organic field effect transistors (OFET) by using gel as dielectric and molecular doping to the active organic semiconductor. In order to compare the performance improvement, Poly (methylmethacrylate) (PMMA) and Poly (3-hexylthiophene-2,5-diyl) P3HT material system were used as a reference. Propylene carbonate (PC) is introduced into PMMA to form the gel for using as gate dielectric. The mobility increases from 5.72×10⁻³ to 0.26 cm² V s^–1 and operation voltage decreases from −60 to −0.8 with gel dielectric. Then, the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) is introduced into P3HT via co-solution. The mobility increases up to 1.1 cm² V s^–1 and the threshold voltage downs to −0.09 V with doping. The increase in performance is discussed in terms of better charge inducing by high dielectric properties of gel and trap filling due to the increased carrier density in active semiconductor by molecular doping.     

Solution processable organic p–n junction bilayer vertical photodiodes

Organic p–n bilayer photodiodes were produced by solution casting poly(3-hexylthiophene) (P3HT) from chlorobenzene and phenyl-C₆₁-butyric acid methyl ester (PCBM):poly(4-chlorostyrene) (PClS) blends from the nearly orthogonal solvent dichloromethane onto flexible indium tin oxide (ITO)/polyester as a substrate. This is the first demonstration of PCBM–inert polymer blends for such a device. The electron mobility of a 90% PCBM–10% PClS blend was 3.5 × 10^?3 cm²/V s in a field-effect transistor. The diodes showed a rectification ratio of 2.0 × 10³ at ±2.0 V with a forward bias current density as high as 340 μA/cm² at 2.0 V in the dark. Irradiation with various light sources (0.013–291 mW/cm²) under ambient atmosphere generated a linear increase in photocurrent. Photodiodes with thinner active layers showed larger photocurrent and relative photoresponse, probably because of lower series resistance and lower recombination probability. The reverse bias response was less dependent on device area than the forward bias response. Photocurrents from multiple devices in parallel were additive as expected. The results demonstrate a simple fabrication route to light detectors compatible with solution processes and flexible substrates.     

Effective mobility in amorphous organic transistors: Influence of the width of the density of states

The temperature dependence of poly(3-hexylthiophene-2,5-diyl) (P3HT)/polystyrene (PS) blend organic transistor current/voltage (I–V) characteristics has been experimentally and theoretically studied. The planar transistors, realized by drop casting the P3HT/PS ink, exhibit high mobilities (over 5 × 10⁻³ cm² V⁻¹ s⁻¹) and good overall characteristics. A transistor model accounting for transport mechanisms in disordered organic materials was used to fit the measured characteristics. Using a single set of parameters, the measured effective mobility versus gate bias, either increasing or decreasing with the gate bias depending on temperature, is well reproduced over a wide temperature range (130–343 K). A Gaussian density of states width of 0.045 eV was determined for this P3HT/PS blend. The transistor I–V characteristics are very well described considering disordered material properties within a self-consistent transistor model.     

Charge carrier mobility and lifetime of organic bulk heterojunctions analyzed by impedance spectroscopy

Charge carrier diffusion and recombination in an absorber blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) with indium tin oxide (ITO) and aluminium contacts have been analyzed in the dark by means of impedance spectroscopy. Reverse bias capacitance exhibits Mott–Schottky-like behavior indicating the formation of a Schottky junction (band bending) at the P3H:PCBM-Al contact. Impedance measurements show that minority carrier (electrons) diffuse out of the P3HT:PCBM-Al depletion zone and their accumulation contributes to the capacitive response at forward bias. A diffusion–recombination impedance model accounting for the mobility and lifetime parameters is outlined. Electron mobility results to be 2 × 10⁻³ cm² V⁻¹ s⁻¹ and lifetime lies within the milliseconds timescale.     

Low power flexible organic thin film transistors with amorphous Ba0.7Sr0.3TiO3 gate dielectric grown by pulsed laser deposition at low temperature

We deposited amorphous Ba_0.7Sr_0.3TiO₃ (BST) on silicon and plastic substrate under 110 °C by pulsed laser deposition (PLD) and use it as the dielectric of the organic transistor. Depends on the thickness of BST layer, the highest mobility of the devices can achieve 1.24 cm² V^?1 s^?1 and 1.01 cm² V^?1 s^?1 on the silicon and polyethylene naphthalate (PEN) substrate, respectively. We also studied the upward and downward bending tests on the transistors and the dielectric thin films. We found that the BST dielectric pentacene transistor can maintain the mobility at 0.5 cm² V^?1 s^?1 or higher while the bending radius is around 3 mm in both upward and downward bending. Our finding demonstrates the potential application of PLD growth high-k dielectric in the large area organic electronics devices.     

All-conjugated diblock copolymer of poly(3-hexylthiophene)-block-poly(3-phenoxymethylthiophene) for field-effect transistor and photovoltaic applications

The electronic properties, morphology and optoelectronic device characteristics of conjugated diblock copolythiophene, poly(3-hexylthiophene)-block -poly(3-phenoxymethylthiophene) (P3HT-b-P3PT), are firstly reported. The polymer properties and structures were explored through different solvent mixtures of chloroform (CHCl₃), dichlorobenzene (DCB), and CHCl₃:DCB (1:1 ratio). The absorption maximum (λ_max) of P3HT-b-P3PT prepared from DCB was around 554 nm with a shoulder peak indicative for the highly crystalline structure around 604 nm while that from CHCl₃ was 516 nm without the clear shoulder peak. The field-effect hole mobility of P3HT-b-P3PT increased from ～6.0 × 10^?3, ～8.0 × 10^?3 to ～2.0 × 10^?2 cm² V^?1 s^?1 as the DCB content in the solvent mixture enhanced. The AFM images suggested that the highly volatile CHCl₃ processing solvent led to the amorphous structure, on the other hand, less volatile DCB resulted in the largely crystalline structure of the P3HT-b-P3PT. Such difference on the polymer structure and hole mobility led to the varied power conversion efficiency (PCE) of the photovoltaic cells fabricated from the blend of P3HT-b-P3PT/[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) (1:1, w/w): 1.88 (CHCl₃), 2.13 (CHCl₃:DCB (1:1)), and 2.60% (DCB). The PCBM blend ratio also significantly affected the surface structure and the solar cell performance. The PCE of polymer/PCBM could be improved to 2.80% while the ratio of polymer to PCBM went to 1:0.7. The present study suggested that the surface structures and optoelectronic device characteristics of conjugated diblock copolymers could be easily manipulated by the processing solvent, the block segment characteristic, and blend composition.     

Influence of aluminium electrode preparation on PCE values of polymeric solar cells based on P3HT and PCBM

The main goal of the paper was investigation of influence of aluminum electrode preparation via thermal evaporation (TE) and the magnetron sputtering (MS) on power conversion efficiency (PCE) of polymeric solar cells. The photovoltaic properties of such three kinds devices based on poly(3-hexylthiophene-2,5-diyl) (P3HT) as ITO/P3HT/Al, ITO/P3HT:PCBM (1:1, w/w)/Al and ITO/PEDOT:PSS/P3HT:PCBM (1:1, w/w)/Al were investigated. For the constructed devices impedance spectroscopy were analyzed. For devices lack of PEDOT:PSS layer or lack of PCBM, photovoltaic parameters were very low and similar to the parameters obtained for device with Al electrode prepared by magnetron sputtering. The devices comprising PEDOT:PSS with P3HT:PCBM showed the best photovoltaic parameters such as a V_OC of 0.60 V, J_SC of 4.61 mA/cm², FF of 0.21, and PCE of 5.7 × 10^?1%.     

High field-effect mobility from poly(3-hexylthiophene) thin-film transistors by solvent–vapor-induced reflow

Room-temperature exposure of spin-coated poly(3-hexylthiophene) (P3HT) films to ortho-dichlorobenzene vapor increases the field-effect mobility of the P3HT organic thin-film transistors (OTFTs). The mobility increases moderately with unsaturated vapor exposure, owing to increased crystallinity of the P3HT films; on the other hand, the mobility increases abruptly with saturated vapor exposure, to 0.11 cm²/V s. The saturated vapor exposure causes the P3HT films to reflow, leaving in the active area approximately 2–3 P3HT monolayers whose molecular ordering is enhanced by the flow-generated shear against the gate dielectric. Although the reflowed OTFTs degrade in air much faster than do the non-reflowed OTFTs due to the susceptibility of the ultra-thin reflowed films, they become highly stable when encapsulated, obtaining a lifetime of more than 3000 h.     

On the stability of the electrical and photoelectrical properties of P3HT and P3HT:PCBM blends thin films

New photoelectrical properties of poly(3-hexylthiophene-2,5-diyl), highly regioregular (P3HT): Methanofullerene Phenyl-C₆₁-Butyric-Acid-Methyl-Ester [60] PCBM films were putted in evidence. For the first time the electrical conductivity dependencies on temperature in dark and under different illuminations were studied for the P3HT and P3HT:PCBM blend films. These dependencies shows reversible processes and a high sensitivity of the P3HT and P3HT:PCBM to light. The decrease of the resistivity at the exposure to light is of 18% for P3HT films and of 20% for P3HT:PCBM blend films, for a irradiation under 0.5 W/m² white light at room temperature. By adding the fullerene molecules, in the 1:0.8 polymer:fullerene ratio, the electrical resistivity at room temperature of the blend films decrease compared to the polymer film by 40% in dark, and by 68% under 250 W/m² white light irradiance.The decrease of the resistivity with the temperature is more pronounced in the presence of light indicating a photon activated process.The existence of the open circuit voltage was evidenced even for planar geometry photodiodes and the values of the open circuit voltage under 1000 W/m² solar light illumination are coherent with the difference between the work functions of the electrodes.     

Increase in hole mobility in poly (3-hexylthiophene-2,5-diyl) films annealed under electric field during the solvent drying step

Higher electrical charge carrier mobility in polymer semiconductor films is important to build electronic and opto-electronic devices with improved performance. Application of electric field of the order of 2000 V cm⁻¹ during the solvent drying step for the formation of poly (3-hexyl thiophene-2,5-diyl) (P3HT) film is shown to significantly increase the hole carrier mobility. The reasons for increase in mobility by this novel technique are investigated in this paper. The X-ray diffraction measurements confirm the increase in crystallinity of the films for electric-field annealed samples, while the analysis of the data shows increase in the size of the ‘crystallites’ in those films. The current density–voltage data corresponding to the space charge limited currents at various low temperatures for hole-only devices with P3HT film when fitted to the empirical model for electric-field annealed samples, show an increase in zero field mobility (μ₀) and correspondingly a decrease in activation energy (E_a) and the field dependence pre-factor (γ). The data fitted to the Gaussian disorder model also shows a decrease in the energetic disorder (σ) in the polymer films due to electric-field annealing – indicative of increased ordering of molecules in those films. The analysis confirms the improvement of ordering of the polymer in the film formed due to application of electric field during the solvent drying step of the film formation – a simple processing technique which may be implemented to fabricate higher mobility polymer films for building improved organic electronic devices.     

Efficient ternary blend polymer solar cells with a bipolar diketopyrrolopyrrole small molecule as cascade material

We present a ternary strategy to enhance the power conversion efficiency (PCE) of bulk heterojunction polymer solar cells (PSCs) with a bipolar small molecule as cascade material. A bipolar diketopyrrolopyrrole small molecule (F(DPP)₂B₂), as the second electron acceptor, was incorporated into poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C₆₁-butyric-acidmethyl-ester (PC₆₁BM) blend to fabricate ternary blend PSCs. The introduction of the bipolar compound F(DPP)₂B₂ can not only broaden the light absorption of the active layer because of its absorption in near infrared region but also play a bridging role between P3HT and PC₆₁BM due to the cascaded energy level structure, thus improving the charge separation and transportation. The optimized ternary PSC with 5 wt% F(DPP)₂B₂ content delivered a high PCE of 3.92% with a short-circuit current density (J_sc) of 9.63 mA cm⁻², an open-circuit voltage (V_oc) of 0.62 V and a fill factor (FF) of 64.90%, showing an 23% improvement of PCE as compared to the binary systems based on P3HT:PC₆₁BM (3.18%) or P3HT:F(DPP)₂B₂ (3.17%). The results indicate that the ternary PSCs with a bipolar compound have the potential to surpass high-performance binary PSCs after carefully device optimization.     

Evolution in crystal structure and electrical performance of thiophene-based polymer field effect transistors: A remarkable difference between thermal and solvent vapor annealing

We report the various conformational structures of long pendant side-chains, and the effects of thermal and solvent vapor annealing (SVA) with the corresponding charge carrier mobilities of thiophene-based conjugated polymers, poly[5,5′-bis(3-dodecyl-2-thienyl)-2,2′-bithiophene] (PQT-12) and poly(4,4′-bis-decyloxymethylquaterthiophene) (POQT), by correlated study of their extraordinary polymorphic crystal structures. In substitution for alkyl chains in polythiophenes, ether alkyl chains induce a favorable non-covalent interaction between the oxygen and sulfur atoms and help the polymer chains planar with lower torsion angles between conjugated backbone units showing a reduced π–π stacking distance. However, the flexibility and conformational freedom with such long side-chains dominantly induce polymorphic crystallites from bent and extended side-chains. Especially, POQT exhibit two polymorphic crystallite phases in a similar ratio probably due to the increased freedom of ether alkyl chains. Therefore, the field effect mobility of POQT is decreased gradually with the increase of annealing temperature from 0.024 (at 80 °C) to 3.96 × 10⁻⁴ cm²/V s (at 170 °C). Contrary to the thermal annealing method, solvent-vapor-annealed POQT films show highly ordered and single-phase crystallites with edge-on orientation to the substrate, which ultimately provides an effectively improved charge carrier mobility from 0.023 (pristine) to 0.076 cm²/V s after adequate solvent vapor exposure.     

Effects of semiconductor/dielectric interfacial properties on the electrical performance of top-gate organic transistors

We investigated the effects of varying the properties of the interface between a semiconductor P3HT layer and a dielectric Cytop™ layer on the performances of the resulting transistor devices by comparing the mobilities of devices prepared with bottom gate/bottom contact or top gate/bottom contact architectures. The reduced channel roughness that arose from the thermal annealing step dramatically enhanced the field-effect mobility, yielding the highest mobility yet obtained for a top-gate transistor: 0.12 cm²/V s. High-performance OFETs may be fabricated by controlling the channel roughness and the properties of the interface between the semiconductor and the gate dielectric.     

Low-voltage,high speed inkjet-printed flexible complementary polymer electronic circuits

We report the development of high-performance inkjet-printed organic field-effect transistors (OFETs) and complementary circuits using high-k polymer dielectric blends comprising poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) and poly(methyl methacrylate) (PMMA) for high-speed and low-voltage operation. Inkjet-printed p-type polymer semiconductors containing alkyl-substituted thienylenevinylene (TV) and dodecylthiophene (PC12TV12T) and n-type P(NDI2OD-T2) OFETs showed high field-effect mobilities of 0.1–0.4 cm² V^?1 s^?1 and low threshold voltages down to 5 V. These OFET properties were modified by changing the blend ratio of P(VDF-TrFE) and PMMA. The optimum blend – a 7:3 wt% mixture of P(VDF-TrFE) and PMMA – was successfully used to realize high-performance complementary inverters and ring oscillators (ROs). The complementary ROs operated at a supplied bias (V_DD) of 5 V and showed an oscillation frequency (f_osc) as high as ～80 kHz at V_DD = 30 V. Furthermore, the f_osc of the complementary ROs was significantly affected by a variety of fundamental parameters such as the electron and hole mobilities, channel width and length, capacitance of the gate dielectrics, V_DD, and the overlap capacitance in the circuit configuration.     

Characterization of solution processed,p-doped films using hole-only devices and organic field-effect transistors

We report a solution processed, p-doped film consisting of the organic materials 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA) as the electron donor and 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluorotetracyanoquinodimethane (F3TCNQ-Adl) as the electron acceptor. UV–vis–NIR absorption spectra identified the presence of a charge transfer complex between the donor and acceptor in the doped films. Field-effect transistors were used to characterize charge transport properties of the films, yielding mobility values. Upon doping, mobility increased and then slightly decreased while carrier concentration increased by two orders of magnitude, which in tandem leads to conductivity increasing from 4 × 10^?10 S/cm when undoped to 2 × 10^?7 S/cm at 30 mol% F3TCNQ-Adl. The hole density was calculated based on mobility values extracted from OFET data and conductivity values extracted from bulk I–V data for the MTDATA: x mol% F3TCNQ-Sdl films. These films were then shown to function as the hole injection/hole transport layer in a phosphorescent blue OLED.     

Understanding the role of organic polar solvent induced nanoscale morphology and electrical evolutions of P3HT:PCBM composite film

We investigated the effect of organic polar solvent on the properties of [6,6]-phenyl-C₇₁-butyric acid methyl ester (PCBM) films and poly(3-hexylthiophene) (P3HT):PCBM blend films employed as active layer in organic photovoltaic. The nanoscale morphology and the electrical characteristics of the P3HT:PCBM film can be controlled through organic polar solvent exposure, which exhibited with a short-circuit current density of 8.64 mA/cm², an open circuit voltage of 0.63 V, and a power conversion efficiency of 3.29% under AM 1.5 illumination with a light intensity of 100 mW/cm². By exposing the active layer films to organic polar solvent a favorable phase separation in the P3HT:PCBM films is obtained. The improved power conversion efficiency can be to the high conductivity and high surface area of the P3HT:PCBM layer treated with organic polar solvent.     

Aggregation,crystallization, and resistance properties of poly(3-hexylthiophene-2,5-diyl) solid films gel-cast from CHCl3/p-xylene mixed solvents

In this study we found that the gelation time and crystallinity of P3HT solid films are adjustable when aging and casting from CHCl₃/p-xylene mixed solvents. After aging for 36 h in pure p-xylene, CHCl₃, or various mixtures of the two as cosolvents, we found that the solid P3HT film gel-cast from 20 vol% CHCl₃ had the highest degree of crystallinity of its main chain (ϕ_m = 0.54), highest melting point of its main chain (T_m = 232.7 °C), fastest gelation time (30 min), largest melting enthalpy of its main chain (ΔH_m = 19.81 J g⁻¹), and lowest resistance (R_P = 0.76 MΩ); the latter value was three orders and one order of magnitude lower than those of the films cast from pure CHCl₃ (ca. 110 MΩ) and pure p-xylene (ca. 4.4 MΩ), respectively. In differential scanning calorimetry scans, we attribute the presence of melting peaks near 75 °C to the solid-to-solid phase transition of the side chain crystallites of P3HT, thereby affecting the aggregation of the P3HT main chain and resulting in the changes in resistance, crystallinity, melting enthalpy, and melting point of the gel-cast P3HT solid films.