Shree Prakash Tiwari

Dithienopyrrole-based donor–acceptor copolymers: low band-gap materials for charge transport, photovoltaics and electrochromism

A series of highly soluble donor–acceptor (D–A) copolymers containing N-(3,4,5-tri-n-decyloxyphenyl)-dithieno[3,2-b:2′,3′-d]pyrrole (DTP) or N-(2-decyltetradecyl)-dithieno[3,2-b:2′,3′-d]pyrrole (DTP′) as donor and three different acceptors, 4,7-dithien-2-yl-[2,1,3]-benzothiadiazole, 4,9-dithien-2-yl-6,7-di-n-hexyl-[1,2,5]thiadiazolo[3,4-g]quinoxaline and 4,8-dithien-2-yl-2λ4δ2-benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole (BThX, X = BTD, TQHx2, BBT, respectively) were synthesized by Stille coupling polymerizations. The optical and electrochemical properties of these copolymers were investigated, along with their use in field-effect transistors and photovoltaic devices. The band gaps (eV) estimated from UV-vis-NIR spectra and electrochemical measurements of the copolymers varied from ca. 1.5–0.5 eV, and were consistent with quantum-chemical estimates extrapolated using density functional theory. Oxidative and reductive spectroelectrochemistry of the copolymers indicated they can be both p-doped and n-doped, and three to four differently colored redox states of the polymers can be accessed through electrochemical oxidation or reduction. The DTP-BThBTD and DTP-BThTQHx2 copolymers exhibited average field-effect hole mobilities of 1.2 × 10−4 and 2.2 × 10−3 cm2/(Vs), respectively. DTP-BThBBT exhibited ambipolar field-effect characteristics and showed hole and electron mobilities of 1.2 × 10−3 and 5.8 × 10−4 cm2/(Vs), respectively. Bulk heterojunction photovoltaic devices made from blends of the copolymers with 3′-phenyl-3′H-cyclopropa[1,9](C60-Ih)[5,6]fullerene-3′-butanoic acid methyl ester (PCBM) (1:3 weight ratio) exhibited average power conversion efficiencies as high as 1.3% under simulated irradiance of 75 mW/cm2.

Dithienopyrrole–quinoxaline/pyridopyrazine donor–acceptor polymers: synthesis and electrochemical, optical, charge-transport, and photovoltaic properties

Soluble alternating copolymers of N-(3,4,5-tri-n-dodecyloxyphenyl)dithieno[3,2-b:2′,3′-d]pyrrole donor groups and 2,3-di-n-decylquinoxaline, 2,3-di-n-decylpyrido[3,4-b]pyrazine, 2,3,6,7-tetrakis(n-decyloxy)benzo[a,c]phenazine, or 2,3,6,7-tetrakis(n-decyloxy)dibenzo[f,h]pyrido[4,3-b]quinoxaline acceptors were synthesised using Stille coupling reactions. Experimental absorption maxima in THF range from 645 to 770 nm. These optical data, along with the results of quantum-chemical calculations and electrochemical measurements, show that, as expected, the pyridopyrazine moiety acts as a stronger acceptor than quinoxaline and that the extended species benzophenazine and dibenzopyridoquinoxaline are stronger acceptors than quinoxaline and pyridopyrazine, respectively. Modest average hole mobilities of up to ca. 3.0 × 10−4 cm2 V−1s−1 were obtained in field-effect transistors. Bulk heterojunction photovoltaic devices made from blends of the benzo[a,c]phenazine-based polymer with 3′-phenyl-3′H-cyclopropa[1,9](C60-Ih)[5,6]fullerene-3′-butanoic acid methyl ester (1 : 3 weight ratio) exhibited average power conversion efficiencies up to 1.4%.

Solution-Processed n-Type Organic Field-Effect Transistors With High on / off Current Ratios Based on Fullerene Derivatives

Solution-processed n-type organic field-effect transistors (OFETs) based on the fullerene derivative {6}-1-(3-(2- thienylethoxycarbonyl)-propyl)-{5}-l-phenyl-[5,6]-C61 (TEPP) and phenyl-C61-butyric acid methyl ester (PCBM) in a multiring source/drain structure are reported. Devices with TEPP show high electron mobility up to 7.8 x 10-2 cm2/Vs in the saturation regime for bottom-contact OFETs with Au S/D electrodes with a solution-processed fullerene derivative. The ON/OFF ratios reported in this letter, which are in the range of 105 -106, are among the highest values reported for such devices. This mobility is always higher compared to PCBM devices prepared in identical conditions. The mobility of TEPP and PCBM increased with increasing temperatures in the range of 100-300 K with activation energy of 78 and 113 meV, respectively, which suggests that the thermally activated hopping of electrons is dominant in TEPP.

Determining ionizing radiation using sensors based on organic semiconducting material

The use of organic semiconducting material sensors as total dose radiation detectors is proposed, wherein the change in conductivity of an organic material is measured as a function of ionizing radiation dose. The simplest sensor is a resistor made using organic semiconductor. Furthermore, for achieving higher sensitivity, organic field effect transistor (OFET) is used as a sensor. A solution processed organic semiconductor resistor and an OFET were fabricated using poly 3-hexylthiophene (P3HT), a p-type organic semiconductor material. The devices are exposed to Cobalt-60 radiation for different total dose values. The changes in electrical characteristics indicate the potential of these devices as radiation sensors.

Low-voltage pentacene organic field-effect transistors with high-κ HfO2 gate dielectrics and high stability under bias stress

Low-voltage pentacene organic field-effect transistors are demonstrated (operating voltage of −3 V) with high-κ hafnium dioxide gate dielectrics grown by atomic layer deposition at 200 °C. A high hole mobility of 0.39 cm2/V s with low threshold voltage (<−0.5 V) and low subthreshold slope of 120 mV/dec is achieved with a HfO2 dielectric layer modified with a phosphonic acid based treatment. A high value of 94.8 nF/V s is obtained for the product of mobility and capacitance density. The devices show excellent bias stress stability with or without the phosphonic acid at the HfO2 gate dielectric surface.

Low-voltage solution-processed n-channel organic field-effect transistors with high-k HfO2 gate dielectrics grown by atomic layer deposition

High performance solution-processed n-channel organic field-effect transistors based on [6,6]-phenyl C61 butyric acid methyl ester with low operating voltages (3 V) are demonstrated using a high-k hafnium dioxide gate dielectric grown by atomic layer deposition. Devices exhibit excellent n-channel performance with electron mobility values up to 0.14 cm2/V s, threshold voltages of ∼0.3 V, current on/off ratios >105, and very low values of subthreshold slope (∼140 mV/decade).

Study of electrical performance and stability of solution-processed n-channel organic field-effect transistors

Solution processed n-channel organic field-effect transistors based on [6,6]-phenyl C61 butyric acid methyl ester with high mobility and low contact resistance are reported. Ca, Au, or Ca capped with Au (Ca/Au) was used as the top source/drain electrodes. The devices with Ca electrodes exhibit excellent n-channel behavior with electron mobility values of 0.12 cm2/V s, low threshold voltages (∼2.2 V), high current on/off ratios (105–106) and subthreshold slopes of 0.7 V/decade. By varying the channel lengths (25–200 μm) in devices with different metal/semiconductor interfaces, the effect of channel length scaling on mobility is studied and the contact resistance is extracted. The width-normalized contact resistance (RCW) for Au (12 kΩ cm) is high in comparison to Ca (7.2 kΩ cm) or Ca/Au (7.5 kΩ cm) electrodes at low gate voltage (VGS=10 V). However, in the strong accumulation regime at high gate voltage (VGS=30 V), its value is nearly independent of the choice of metal electrodes and in a range of 2.2–2.6 ...

Solution-Processed Bootstrapped Organic Inverters Based on P3HT With a High-

In this letter, the integration of a high-k gate dielectric has been demonstrated for achieving low-operating-voltage organic field-effect transistors (OFETs) and circuits based on solution-processed poly(3-hexylthiophene) (P3HT). We have successfully demonstrated all-p-type organic circuits based on P3HT operating at below 4 V supply voltage. The switching behavior is improved by using the bootstrapping technique, with the bootstrapped inverter showing good results with a dc gain (A v) of - 1.7 and V OH and V OL values of 3.3 and 0.35 V, respectively. The output swing of the bootstrapped inverter is improved by about 40% when compared to that of simple all-p-type inverters, as demonstrated by using experimental characterizations.

k

The field emission of a carbon nanotube (CNT) pillar array has been improved significantly by plasma treatment in a mixture of hydrogen and nitrogen gases. The plasma treatment for 30s on a pillar array decreased the turn-on electric field from 0.48to0.37V∕μm and increased the field enhancement factor from 6200 to 6900. The emission current density increased by a factor of ≈40. We report in this letter the technique of generating nanotips on CNT pillars with an enormous potential to become a tool for the control and manipulation of CNTs and nanostructures.

Gate Dielectric Material

Perylene-3,4,9,10-tetracarboxylic diimides (PDI) have been linked to norbornene through either an imide or a “bay” position. These PDI-functionalised norbornenes are readily polymerised using a ruthenium ring-opening metathesis polymerisation (ROMP) initiator. In one case the polymerisation is shown to be well controlled with a linear dependence of molecular weight on the monomer/initiator ratio. For the polymers with PDI–norbornene linkages through the imide nitrogen, UV-vis spectroscopy suggests significant PDI aggregation both in dilute solution and the solid state, a powder X-ray diffraction peak attributable to π-stacking is seen, and weak n-channel field-effect transistor behavior (electron mobilities <5 × 10−5 cm2 V−1 s−1) was observed. In contrast, the “bay”-linked polymer shows essentially monomer-like UV-vis spectra in both solution and the solid state, no X-ray evidence for π-stacking, and no measurable transistor behaviour. The polymers were used as acceptors in bulk heterojunction solar cells in combination with poly(3-hexylthiophene): low power conversion efficiencies (≤0.38%) were obtained, largely due to low short-circuit currents, again with the “bay”-linked polymer giving the poorest performance.