High mobility organic field-effect transistors based on defect-free regioregular poly(3-hexylthiophene-2,5-diyl)

We report on organic field-effect transistors (OFETs) prepared using defect free (100% regioregular) poly(3-hexylthiophene-2,5-diyl) (DF-P3HT) as semiconductor and cross-linked poly(vinyl alcohol) (cr-PVA) as gate insulator. High field-effect mobility (μ_FET) of 1.2 cm² V⁻¹ s⁻¹ is obtained and attributed to the absence of regioregularity defects. These transistors have transconductance of 0.35 μS and the DF-P3HT film shows larger crystallites (∼80 Å) than a highly regioregular (>98%) material (∼32 Å). Devices with increased μ_FET (2.8 cm² V⁻¹ s⁻¹) could be obtained at the expense of the On-Off current ratio, which was reduced by one order of magnitude, when poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) treatment was applied to the dielectric surface. Our results suggest that the interaction of charged sites at the dielectric surface with regioregularity defects of the P3HT is an important factor degrading μ_FET even at very low concentration of regioregularity defects.     

Field-effect transistors based on poly(3-hexylthiophene): Effect of impurities

Organic field-effect transistors (OFETs) based on regioregular poly(3-hexylthiophene)s (P3HT)s have been studied as a function of the amount of impurities in the active polymer. P3HTs have been synthesized via a nickel-initiated cross-coupling polymerization and successively purified by a series of Soxhlet extractions with methanol, hexane and chloroform. At each stage, the amount of impurities was quantified by means of ¹H nuclear magnetic resonance (NMR) spectroscopy, Rutherford backscattering spectroscopy (RBS) and particle induced X-ray emissions (PIXE). Traces of Ni, Cl, Mg, Ca, Fe and Zn could be detected in non-fully purified P3HTs. The presence of impurities in the different fractions of P3HT is shown to affect not only the characteristics of the OFETs but also the photovoltaic performances.     

Efficiency enhancement of polymer solar cells by post-additional annealing treatment

We adopt the post-additional thermal annealing (PATA) process to optimize the performance of the polymer solar cells (PSCs) with an active layer composed of a blend of regioregular poly (3-hexythiophene) (RR-P3HT) and fullerenes. It is found that compared with general annealing process, the crystallinity of RR-P3HT by PATA is enhanced, and the absorption peak is raised obviously at ～500 nm after PATA. With the optimized annealing conditions, the device shows an enhancement of 31% in short circuit current density, 5% in open circuit voltage (Voc), and 11% in the power conversion efficiency (PCE) compared with that of the general annealing device.     

Enhanced pure red electroluminescence intensity of Eu(o-BBA)3(phen) by red dye co-doping and inorganic semiconductor as charge carrier function layer

There is an emission peak at 494 nm in the electroluminescence (EL) of PVK [poly(n-vinylcarbazole)]: Eu(o-BBA)₃(phen) besides PVK exciton emission and Eu³⁺ characteristic emissions. Both the peaking at 494 nm emission and PVK emission influenced the color purity of red emission from Eu(o-BBA)₃(phen). In order to restrain these emissions and obtain high intensity red emission, 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7,-tetramethyljulolidy-9-enyl)-4Hpyran (DCJTB) and Eu(o-BBA)₃(phen) were co-doped in PVK solution and used as the active emission layer. The EL intensity of co-doped devices reached to 420 cd/m² at 20 V driving voltage. The chromaticity coordinates of EL was invariable (x = 0.55, y = 0.36) with the increase of driving voltage. For further improvement of EL intensity, organic–inorganic hybrid devices (ITO/active emission layer/ZnS/Al) were fabricated. The EL intensity was increased by a factor of 2.5 [(420 cd/m²)/(168 cd/m²)] when the Eu complex was doped with an efficient dye DCJTB, and by a factor of ≈4 [(650 cd/m²)/(168 cd/m²)] when in addition ZnS layer was deposited on such an emitting layer prior to evaporation of the Al cathode.     

Electronic structures and chemical reactions at the interface between Li and regioregular poly (3-hexylthiophene)

Interfaces between metals and π-conjugated polymers play an important role in the organic electronic and optoelectronic devices such as polymer-based light-emitting diodes (PLEDs) and photovoltaic devices. In this study, synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS) have been applied to in situ investigate the chemical reactions and electronic structure during the interface formation of Li on the regioregular poly(3-hexylthiophene) (rr-P3HT) thin films. Upon Li adsorption onto P3HT at 300 K, Li dopes electrons into P3HT, inducing the occurrence of the P3HT band bending. Moreover, Li can diffuse into the subsurface and react with both S and C atoms in the thiophene rings, leading to the formation of Li₂S and Li–C complex. Compared to the interface of Ca/P3HT, the diffusion/reaction depth of Li is much larger at the Li/P3HT interface. Through the investigation of the evolution of core level and valence band spectra together with secondary electron cutoff an energy level alignment diagram at the Li/rr-P3HT interface is derived.     

Charge carrier mobility,bimolecular recombination and trapping in polycarbazole copolymer:fullerene (PCDTBT:PCBM) bulk heterojunction solar cells

Organic photovoltaic devices based on the donor:acceptor blend of poly[N-9″-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) have received considerable attention in recent years due to their high power conversion efficiencies and the ability to achieve close to 100% internal quantum efficiency. However, the highest efficiencies were all attained using active layers of less than 100 nm, which is not ideal for either maximised potential performance or commercial viability. Furthermore, more recent reports have documented significant charge carrier trapping in these devices. In this paper two charge extraction techniques (photo-CELIV and time-of-flight) have been used to investigate the mobility and recombination behaviour in a series of PCDTBT:PCBM devices. The results not only confirm significant charge carrier trapping in this system, but also reveal close to Langevin-type bimolecular recombination. The Langevin recombination causes a short charge carrier lifetime that results in a short drift length. The combination of these two characteristics (trapping and fast bimolecular recombination) has a detrimental effect on the charge extraction efficiency when active layers greater than ∼100 nm are used. This accounts for the pronounced decrease in fill factor with increasing active layer thickness that is typically observed in PCDTBT:PCBM devices.     

Spectroscopic Studies of Photoexcitations in Regioregular and Regiorandom Polythiophene Films

Using a variety of optical probe techniques we studied the steady state and transient dynamics of charged and neutral photoexcitations in thin films of poly‐3‐alkyl thiophene with regioregular order, which forms self‐assembled lamellae structures with increased interchain interaction, as well as regiorandom order that keeps a chain‐like morphology. In regiorandom polythiophene films we found that intrachain excitons with correlated photoinduced absorption and stimulated emission bands are the primary photoexcitations; they give rise to a moderately strong photoluminescence band, and long‐lived triplet excitons and intrachain charged polarons. In regioregular polythiophene films, on the contrary we found that the primary photoexcitations are excitons with much larger interchain component; this results in lack of stimulated emission, vanishing intersystem crossing, and a very weak photoluminescence band. The long‐lived photoexcitations in regioregular polythiophene films are interchain excitons and delocalized polarons (DP) within the lamellae, with very small relaxation energy. The characteristic properties of the DP species are thoroughly investigated as a function of the alkyl side group of the polymer backbone, film deposition conditions and solvents used, as well as at high hydrostatic pressure. The quantum interference between the low energy absorption band of the DP species and a series of photoinduced infrared active vibrations, which give rise to antiresonances that are superimposed on the electronic absorption band is studied and explained by a Fano‐type interference mechanism, using the amplitude mode model.     

Optical,electrical and mechanical properties of indium tin oxide on polyethylene terephthalate substrates: Application in bulk-heterojunction polymer solar cells

We investigated optical, electrical and mechanical properties of indium tin oxide (ITO) on flexible polyethylene terephthalate (PET) substrate, considering bulk-heterojunction (BHJ) polymer solar cells applications. Encapsulation of flexible solar cells with the architecture PET/ITO/PEDOT:PSS/P3HT:PCBM (or P3HT:PCBM:AZ-NDI-4)/Al was done by direct brush-painting with nail enamel. Active cell layer blends of [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with regioregular or regiorandom poly(3-hexylthiophene-2,5-diyl) (P3HT) were applied. Additionally for this role the mixture of regioregular P3HT:PCBM with naphthalene diimide–imine with four thiophene rings AZ-NDI-4 was tested. Obtained photovoltaic (PV) and optical (UV–vis) results of the flexible polymer solar cells were compared with the same architecture of devices on the glass/ITO substrate.     

Di(2-pyridyl)ketone stabilized titanium dioxide nanoparticles for the room temperature processed electron transporting layer in organic photovoltaics

Monodisperse TiO₂ nanoparticles are obtained through hydrolysis of titanium butoxide in the presence of di(2-pyridyl)ketone (DPK) and para-toluenesulfonic acid. The DPK ligand stabilized the surface of the TiO₂ nanoparticle through complexation with TiO₂. DPK stabilized TiO₂ (TNP-DPK) can be dispersed without aggregation in alcoholic solutions at concentrations higher than 1 M. The synthesized particles have 4–5 nm size and spherical shape at amorphous phase. The atomic force microscope image reveals that only 0.1 wt% of TNP-DPK solution can form a conformal and dense film on top of the active layer. The TNP-DPK solution is used for an electron transporting layer (ETL) in organic photovoltaics (OPV) that utilizing poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)] (PTB7-Th) as a photoactive layer. The power conversion efficiency of the OPV is significantly improved from 7.18% to 9.08% by inserting the TNP-DPK layer between photoactive layer and Al electrode. Based on the internal quantum efficiency and transient photo voltage experiments, the TNP-DPK layer is found to improve the charge collection efficiency and reduce the charge recombination at the active layer/electrode interface. These results clearly show that the solution processed TNP-DPK layer can play a role as an efficient ETL in OPVs.     

Design of High-Performance Regioregular Polythiophenes for Organic Thin-Film Transistors

The performance of a regioregular polythiophene semiconductor for solution-processed organic thin-film transistors (OTFTs) is critically dependent on its ability to self-organize from solution and its stability against p-doping by oxygen. Structural features that promote lamellar ordering and delicately curtail the /spl pi/-conjugation of regioregular polythiophene system would enable achievement of high field-effect mobility in air. Molecular design principles and structure-property correlation studies that lead to the design of a solution-processed, all-round high-performance polythiophene semiconductor system (PQT) for OTFTs are discussed. Mobility to 0.14 cm/sup 2/ V/sup -1/ s/sup -1/ and current on/off ratio of 10/sup 7/, together with other desirable thin-film transistor (TFT) properties have been obtained with this class of organic semiconductors in OTFTs under ambient fabrication conditions.     

Photosensitive Polymer Thin-Film FETs Based on Poly(3-octylthiophene)

The effects of white light on the electrical performance of polymer thin-film transistors (PTFTs) based on regioregular poly(3-octylthiophene) (P3OT) are investigated. Upon illumination, a significant increase in the PFET's drain current is observed with a maximum photosensitivity of 10/sup 4/ in the subthreshold operation and a broad-band responsivity with a maximum value of 160 mA/W at irradiance of 1.7 mW/cm/sup 2/ and at low gate biases. The photosensitivity decreases with the increase in the absolute gate bias. The simultaneous control of the device with both the gate voltage and illumination is possible at low irradiances of <0.7 mW/cm/sup 2/. It is found that the illumination effectively decreases the threshold voltage of the device, but it does not change the field-effect mobility. Using a trap model, it is shown that the narrow layers close to the drain and source contacts with high concentrations of defects are two possible regions for photogeneration of excitons and separation of charges. Using the theory of space-charge limited conduction, the extracted band mobility for P3OT is 0.08 cm/sup 2//V/spl middot/s, while a mobility of 8/spl times/10/sup -5/cm/sup 2//V/spl middot/s is found for the regions next to the source and drain contacts. The PTFT's high photosensitivity at zero gate voltage suggests a simple design of low-voltage, high-sensitivity two-terminal photodetectors for applications in large-area flexible optoelectronics.     

Resistive Switching in a Printed Nanolayer of Poly(4-vinylphenol)

Resistive switching in organic resistive switches fabricated with a sandwich structure of indium tin oxide (ITO)-coated polyethylene terephthalate (PET)/poly(4-vinylphenol) (PVP)/silver (Ag) is reported. A single layer of PVP was used as an active layer in the sandwich structure between the two electrodes. The active layer of the polymer was atomized with the electrohydrodynamic atomization technique on the ITO-coated PET. The film thickness of the PVP polymeric layer on the ITO-coated PET was measured to be 110 nm. The surface morphology was characterized by field-emission scanning electron microscopy, and the purity of the film was examined by x-ray photoelectron spectroscopy analysis. Electrical current–voltage (I–V) measurements confirmed the memristive behavior of the sandwich device. The effect of the current compliance (CC) on resistive switching in the fabricated sandwich structure was also explored. The PVP-based organic resistive switch showed a CC-dependent OFF/ON ratio and memory window. Resistive switching memory effects were prominent at low CC up to nanoamps. The as-fabricated device was operated with low operational voltages for both polarities with OFF/ON ratio greater than 100:1. The robustness of the fabricated memristor was checked with multiple voltage sweeps, and the retention time is reported to be over 100 min.     

Polarized photoluminescence and electroluminescence in oriented films of regioregular poly(3-alkylthiophenes)

We report polarized photoluminescence (PL) and electroluminescence (EL) from regioregular poly(3-alkylthiophene) thin films oriented by means of the rubbing technique. With a proper thermal annealing of the rubbed films we have increased the anisotropy reaching values up to 8 both in PL and EL. We have evidenced that the orientation in the rubbing direction is higher for the longest conjugation segments than for the less conjugated ones. Moreover polarized PL study demonstrates that emission takes place after migration of the excitation from shorter, less oriented, to longer, more oriented conjugation segments.     

Hybrid Solar Cells from a Blend of Poly(3‐hexylthiophene) and Ligand‐Capped TiO2 Nanorods

Hybrid bulk heterojunction solar cells based on nanocrystalline TiO₂ (nc‐TiO₂) nanorods capped with trioctylphosphine oxide (TOPO) and regioregular poly(3‐hexylthiophene) (P3HT) are processed from solution and characterized in order to relate the device function (optical absorption, charge separation, and transport and photovoltaic properties) to active‐layer properties and device parameters. Annealing the blend films is found to greatly improve the polymer–metal oxide interaction at the nc‐TiO₂/P3HT interface, resulting in a six‐fold increase of the charge separation yield and improved photovoltaic device performance under simulated solar illumination. In addition, the influence of the organic ligand at the nc‐TiO₂ particle surface is found to be crucial for charge separation. Ligand‐exchange procedures applied on the TOPO‐capped nc‐TiO₂ nanorods with an amphiphilic ruthenium‐based dye are found to further improve the charge‐separation yield at the polymer–nanocrystal interface. However, the poor photocurrents generated in the hybrid blend devices, before and after ligand exchange, suggest that transport within or between nanoparticles limits performance. By comparison with other donor–acceptor bulk heterojunction systems, we conclude that charge transport in the nc‐TiO₂:P3HT blend films is limited by the presence of an intrinsic trap distribution mainly associated with the nc‐TiO₂ particles.     

Efficient fluorescent white organic light-emitting diodes using co-host/emitter dual-role possessed di(triphenyl-amine)-1,4-divinyl-naphthalene

Efficient fluorescent white organic light-emitting diodes with low carrier-injection barriers were fabricated with device structure of indium tin oxide/N,N′-bis-(1-naphthy)-N,N′-diphenyl-1,1′-biphenyl-4-4′-diamine/white emission layer/1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene/lithium fluoride/aluminium. By blending in the blue host of 1-butyl-9,10-naphthalene-anthracene in the emissive layer an efficient electro-luminescent greenish-blue co-host of di(triphenyl-amine)-1,4-divinyl-naphthalene, with the doping of a trace amount of red dye of 4-(dicyano-methylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran, bright and colour-stable white emission with high power-efficiency of 14.6 lm/W at 100 cd/m² or current efficiency of 19.2 cd/A at 300 cd/m² or 18.7 cd/A at 10,000 cd/m² was obtained. The resulted synergistic increase in brightness and efficiency may be attributed to the presence of cascading new routes with comparatively lower electron injection barrier.     

The Effect of Poly(3‐hexylthiophene) Molecular Weight on Charge Transport and the Performance of Polymer:Fullerene Solar Cells

The time‐of‐flight method has been used to study the effect of P3HT molecular weight (M_n = 13–121 kDa) on charge mobility in pristine and PCBM blend films using highly regioregular P3HT. Hole mobility was observed to remain constant at 10^?4 cm²V^?1s^?1 as molecular weight was increased from 13–18 kDa, but then decreased by one order of magnitude as molecular weight was further increased from 34–121 kDa. The decrease in charge mobility observed in blend films is accompanied by a change in surface morphology, and leads to a decrease in the performance of photovoltaic devices made from these blend films.     

Theoretical studies on cyclometalated platinum(II) complexes based on isoquinolinyl azolate: ππ-stacking interaction and photophysical properties

The photophysical properties of four Pt(II) complexes [Pt(Lx)₂], x = 1–4, (1–4), where Lx are 6-t-butyl-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (1), 3,5-di-t-butyl-1-(3-trifluoromethyl-1H-pyrazol-5-yl) isoquinoline (2), 6-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (3), and 4-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (4), are investigated by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Furthermore, the binding interaction in Pt_n stack is studied to discover the influence of different cyclometalated ligand. The calculated results rationalize that the complex 1 exhibits a stack of three molecules rather than the infinite aligned stack. Complexes 1 and 3 present the stronger tendency to form the aligned ππ-stacking interaction as compared with complexes 2 and 4. The dimers of other four complexes, 3a (Pt(L3)(Ma), Ma = 5-(2-pyridyl)-3-trifluoromethylpyrazole), 3b (Pt(L3)(Mb), Mb = 5-(4-phenyl-2-pyridyl)-3-trifluoromethylpyrazole), 3c (Pt(L3)(Mc), Mc = 5-(4-tert-butyl-2-pyridyl)-3-trifluoromethylpyrazole), and 5 (Pt(fppz)₂ fppz = 5-(2-pyridyl)-3-trifluoromethylpyrazole), are also studied to investigate the effect of different aromatic ligand or substituents on the ππ-stacking interaction. The emissions of complexes 1–4 originate from various charge transfer states including the intraligand charge transfer (ILCT) and ligand-to-ligand charge transfer (LLCT) together with the metal-to-ligand charge transfer (MLCT). Finally, the items related with the radiative and nonradiative rate constants are examined. Besides the potential energy profile between the lowest triplet state (³MLCT) and metal centered state (³MC), the deactivation process of the ³MC state via the minimum energy crossing point (MECP) between the ³MC and the ground state (¹S₀) potential surfaces is also explored.     

Phenylimidazole-based homoleptic iridium(III) compounds for blue phosphorescent organic light-emitting diodes with high efficiency and long lifetime

In order to obtain triplet emitters with high stability and efficiency, three homoleptic iridium(III) compounds — specifically, Ir(tpim)₃ (1), Ir(mtpim)₃ (2), and Ir(itpim)₃ (3), where tpim = 1-([1,1′:3′,1″-terphenyl]-2′-yl)-2-(4-fluorophenyl)-1H-imidazole, mtpim = 2-(4-fluorophenyl)-1-(5′-methyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole, and itpim = 2-(4-fluorophenyl)-1-(5′-isopropyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1H-imidazole — were prepared by one-pot reaction of the corresponding phenylimidazole ligand with an Ir(I) complex as a starting material. Compounds 1–3 emit bright sky-blue phosphorescence with λ_max = 459–463 nm and phosphorescent quantum efficiencies of 0.38–0.50. Multi-layer phosphorescent organic light-emitting diodes using compounds 1–3 as the triplet emitters and mCBP (3,3-di(9H-carbazol-9-yl)biphenyl) as the host have been fabricated. Compound 3 doped in the emissive layer demonstrate external quantum efficiency as high as 20.1% at 1000 cd/m². In addition, the device based on compound 1 as an emitter shows a stable lifetime greater than 300 h at 1000 cd/m², which is one of the best results concerning the device lifetime.     

Photovoltaic device performance of highly regioregular fluorinated poly(3-hexylthiophene)

Highly regioregular poly(3-hexylthiophene) derivatives with varying degrees of fluorine substitution on the thiophene moieties have been demonstrated in photovoltaic devices and characterized using ultraviolet and inverse photoelectron spectroscopy. As fluorine content is increased, an increase in ionization energy of 0.3 eV is observed for 50% fluorination compared to non-fluorinated poly(3-hexylthiophene). The electron affinity is observed to increase to a lesser extent with increased fluorination, consistent with a systematic increase in the optical bandgaps of up to 0.12 eV. Bulk heterojunction photovoltaic devices made from polymer:PC₆₁BM blends achieve power conversion efficiencies of 3%, however film morphologies measured using atomic force microscopy indicate that strong phase separation with increasing fluorination limits device performance. UV–vis spectra of thin films of the fluorinated materials exhibit a long tail in the red, extending to longer wavelengths than non-fluorinated poly(3-hexylthiophene). Photovoltaic devices similarly exhibit non-zero quantum efficiency in this region. This behavior has been attributed to a low energy, interchain charge transfer state.