Synthesis and properties of copolymers composed of arylenevinylene and phenothiazine for organic solar cells

A series of new organic semiconducting copolymers composed of {(2E,2'E)-3,3'-[2,5-bis(octyloxy)-1,4-phenylene]-bis[2-(thiophen-2-yl)acrylonitrile]}(OPTAN) and 10(2'-ethylhexylphenothiazine) (PTZ) monomers, (the copolymers are hereafter referred to as poly(OPTAN-co-PTZ)s), were synthesized by using Suzuki coupling polymerization in which the monomer ratios were controlled. An increase in the OPTAN content shifted the peak and onset absorption of the copolymers to the longer wavelength regions, which resulted in a decrease in the band gap energy. The maximum UV absorption of the polymer films was in the range 523-540 nm and the optical band gap energies were in the range 1.90-1.87 eV. Energy levels of the highest occupied molecular orbital (HOMO) of the polymers were determined by cyclic voltammetry (CV). The HOMO energy level of the copolymers was between -5.07 and -5.12 eV. Photovoltaic devices were fabricated by using the copolymers as the p-type donor and C60-PCBM or C70-PCBM as the electron acceptors. The device with poly(50OPTAN-alt-50PTZ) and C70-PCBM showed the best performance among the fabricated devices; the open circuit voltage, short circuit current, fill factor, and maximum power conversion efficiency of this device were 0.79 V, 5.25 mA/cm2, 0.30, and 1.25%, respectively.     

Synthesis and characterization of thin films of poly(3-methyl thiophene) by rf-plasma polymerization

To facilitate synthesis of poly(3-methyl thiophene) thin film by RF-plasma polymerization process, suitable modifications have been done in a RF-sputtering set up. The deposition rate is found to be 3.33 nm/min. The synthesized films are characterized by FTIR, XRD, Ellipsometry, UV-Visible absorption spectroscopy and SEM. From FTIR, the formation of poly(3-methyl thiophene) has been confirmed. It is found that the synthesized polymer is cross-linked. XRD shows the amorphous nature of the prepared polymer film. The optical band gap has been estimated to be 2.14 eV from UV-visible absorption spectrum. Thickness of the polymer films has been measured to be 2000 Å by ellipsometry.     

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

1.IntroductionThere has been much attention paid to nonlinear op-tics.Considerable efforts have been devoted to develop-ing new polymer materials over the past decade becauseof their desirable properties such as large nonlinear op-tical(NLO)coefficient,high responding speed,low pro-duction cost and good mechanical property[1~9].Thepoly(pyrrolyl methines)are regarded as potentially ap-plicative NLO materials[10~14].It is well known thatorganic polymers containing highly conjugated chro-mopho…     

Synthesis, characterization, and nonlinear optical properties of donor–acceptor conjugated polymers and polymer/Ag nanocomposites

Two new donor–acceptor (D–A) conjugated polymers P1 and P2 containing 3,4-didodecyloxythiophene and 1,3,4-oxadiazole units are synthesized via Wittig reaction methodology. Cyclic voltammetry studies reveal that the polymers are both p and n dopable, and possess low-lying LUMO energy levels (?3.34?eV for P1 and ?3.46?eV for P2) and high-lying HOMO energy levels (?5.34?eV for P1 and ?5.27?eV for P2). The optical band gap of the polymers is in the range of 2.25–2.29?eV, calculated from the onset absorption edge. The polymers emit orange to yellow light in the film state when irradiated with a UV light. The synthesized polymers are used to prepare polymer nanocomposites with different wt% of silver nanoparticles. The polymer nanocomposites are characterized by UV–Vis absorption spectroscopy, field emission scanning electron microscopy, and thermogravimetric analysis. Both polymers and polymer/Ag nanocomposites show good thermal stability with onset decomposition temperature around 300?°C under nitrogen atmosphere. The nonlinear optical properties of polymers and polymer/Ag nanocomposites are measured by Z-scan technique. Both polymers and polymer nanocomposites show a good optical limiting behavior. Nearly five times enhancement in the nonlinear optical properties is observed for polymer/Ag nanocomposites. The value of effective two-photon absorption coefficient (β) is in the order of 10^?10–10^?11?m/W. These results indicate that the synthesized polymers (P1 and P2) and their Ag nanocomposites are expected to be good candidates for application in photonic devices.     

Synthesis and photovoltaic properties of a new thiophene-cyclopentadiene-based conjugated polymer

A new low-band gap polymer containing thiophene and cyclopentadiene, poly(5,2,2'-dioctyldithio-phenylcyclopentadiene) (PDTCP), has been synthesized via the FeCl3 oxidative polymerization. PDTCP showed a broad absorption band and a low energy band gap of 1.82 eV. The photoluminescence (PL) of PDTCP is completely quenched upon addition of PCBM indicative of efficient charge transfer. Bulk heterojunction organic photovoltaic cells (OPVs) fabricated from PDTCP as an electron donor showed an open-circuit voltage (V(OC)) of 0.50 V, a short-circuit current (J(SC)) of 1.24 mA/cm2, and the power conversion efficiency of up to 0.20% under AM 1.5 (100 mW/cm2).     

Synthesis and characterization of new dithienosilole-based copolymers for polymer solar cells

A series of dithienosilole-based copolymers, poly [(4,4'-bis(2-hexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-5,5'-diyl] (P1), poly[(4,4'-bis(2-hexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,2'-bithiazole)-5,5'-diyl] (P2), poly[(4,4'-bis(2-hexyl)dithieno[3,2-b:2',3'-d]silole)-2, 6-diyl-alt-(10 -methyl-phenothiazine)-3,7-diyl](P3), poly[(4,4'-bis(2-hexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-9,10-anthracene)-5,5'-diyl] (P4) were synthesized by the Pd-catalyzed Stille polymerization method. Electron-deficient benzothiadiazole and bithiazole units and electron-rich phenothiazine and anthracene moieties were incorporated into the polymer backbone to obtain the broad absorption spectrum and to improve the hole-transporting characteristics, respectively. The polymer solar cell (PSC) was fabricated with a layered structure of ITO/PEDOT:PSS/polymer:C71-PCBM (1:3)/LiF/Al. The best performance of PSC was obtained at P3:C71-PCBM which reaches a power conversion efficiency (PCE) of 1.18%, with a short circuit current density (J(sc)) of 4.75 mA/cm2, an open circuit voltage (V(oc)) of 0.71 V, and a fill factor (FF) of 0.35 under AM 1.5G irradiation (100 mW/cm2).     

Synthesis and characterization of a novel poly(p-phenylenevinylene) derivative containing dibenzothiophene-5,5-dioxide moiety in the main chain with high electron affinity

We synthesized poly(2,8-dibenzothiophene-5,5-dioxide-vinylene-alt-1,4-phenylene-vinylene) (DD-PPV) (oligomer) by the traditional Wittig condensation and characterized it with IR, NMR, UV-vis etc. It is thermally stable and soluble in high polar solvents. Its UV-vis absorption and photoluminescence spectra in N,N-dimethyl-formamide solution show peaks at 369 and 457 nm, respectively. Its fluorescence quantum efficiency in solution is 75%. Its electron affinity is 3.17 eV. The band gap is 2.88 eV. Single-layer light-emitting diode device indium-tin oxide glass/DD-PPV/Aluminum emits greenish blue and the turn-on voltage is approximately 12 V.     

Novel photoactive fluorene-based terpolymers incorporating carbazole for photovoltaic application

A series of novel photoactive conjugated terpolymers based on N-alkyl carbazole, 9,9-didecylfluorene, and bis(thienyl)benzothiadiazole were synthesized by the Pd-catalyzed Suzuki polymerization method with various molar ratios of the carbazole derivatives. Electron-deficient benzothiadiazole and electron-rich carbazole moieties were incorporated into the polymer backbone to obtain the broad absorption spectrum and to improve the hole-transporting characteristics, respectively. The polymer solar cell (PSC) was fabricated with a layered structure of ITO/PEDOT: PSS/polymer:C71-PCBM (1:3)/LiF/Al. The best performance of PSC was obtained at P1:C71-PCBM whose reaches a power conversion efficiency (PCE) of 2.62%, with a short circuit current density (J(SC)) of 8.61 mA/cm2, an open circuit voltage (V(OC)) of 0.82 V, and a fill factor (FF) of 0.37 under AM 1.5 G irradiation (100 mW/cm2).     

Optical properties of poly(vinyl chloride)/poly(ethylene oxide) blend

The relatively high dielectric constant poly(vinyl chloride) (PVC) was blended with poly(ethylene oxide) (PEO) polymer electrolytes to improve their electrical conductivity from the optical spectra of the given polymeric system. The optical properties in the UV–visible region of PVC polymer containing 0%, 20%, 50% and 70% by weight PEO are reported. The optical results obtained were analyzed in terms of the absorption formula for non-crystalline materials. The absorption coefficient and the optical band energy gap (E_opt) have been obtained from direct allowed transitions in k-space at room temperature. The width of the tail of localized states in the band gap (ΔE) was evaluated using the Urbach-edges method. It was found that both (E_opt) and (ΔE) vary with the concentration of the PEO complex in the polymer matrix. In addition, a correlation between the energy gap and the ac-conductivity as a function of PEO complex concentration is also reported.     

Photoelectrochemical polymerization of thiophene on self-assembled RuL2(NCS)2/di(3-aminopropyl)viologen on indium thin oxide

Polythiophene layers were formed on self-assembled monolayers (SAMs)/indium tin oxide (ITO) using photoelectrochemical polymerization. The SAMs on ITO was prepared using Ru(4,4'-dicarboxylic acid-2,2'-bipyridine)2(NCS)2 and di(3-aminopropyl)viologen. The photoelectrochemically polymerized polythiophene layers on SAMs/ITO were characterized using UV-vis. absorption spectroscopy, atomic force microscopy, scanning electron microscopy, and cyclic voltammetry. The polymer layers have thickness of 360 nm, a dense surface morphology, optical gap of 2.38 eV, highest occupied molecular orbital of -5.2 eV and lowest unoccupied molecular orbital of -2.82 eV. In photoelectrochemical cells, the polythiophene on SAMs/ITO electrode showed a photocurrent of 5 microA/cm2.     

Low-temperature synthesis of ZnO nanoparticles for inverted polymer solar cell application

Zinc oxide (ZnO) nanoparticles were synthesized by a simple wet chemical method at low temperature. Morphologies, crystalline structure, and optical transmission of ZnO nanoparticles were investigated. The results showed that the average diameter of as-synthesized ZnO nanoparticles was about 4.9 nm, the nanoparticles were wurtzite-structured (hexagonal) ZnO and had optical band gap of 3.28 eV. Very high optical transmission (>80 %) in visible light region of ZnO nanoparticulate thin films was achieved. Furthermore, an inverted polymer solar cell consisted of ZnO nanoparticles and polymer were fabricated. The device exhibited an open circuit voltage (V_oc) of 0.50 V, a short circuit current density (J_sc) of 1.76 mA/cm², a fill-factor of 38 %, and a power conversion efficiency of 0.42 %.     

Optical properties of ZnO/ZnS and ZnO/ZnTe heterostructures for photovoltaic applications

Although ZnO and ZnS are abundant, stable, and environmentally benign, their band gap energies (3.44, 3.72 eV, respectively) are too large for optimal photovoltaic efficiency. By using band-corrected pseudopotential density functional theory calculations, we study how the band gap, optical absorption, and carrier localization can be controlled by forming quantum-well-like and nanowire-based heterostructures of ZnO/ZnS and ZnO/ZnTe. In the case of ZnO/ZnS core/shell nanowires, which can be synthesized using existing methods, we obtain a band gap of 2.07 eV, which corresponds to a Shockley-Quiesser efficiency limit of 23%. On the basis of these nanowire results, we propose that ZnO/ZnS core/shell nanowires can be used as photovoltaic devices with organic polymer semiconductors as p-channel contacts.     

New anthracene-based semi-conducting polymer analogue of poly(phenylene sulfide): Synthesis and photophysical properties

A new anthracene-based polymer analogue of poly(phenylene sulfide) has been synthesized via Wittig polycondensation. The polymer is soluble and shows a good film quality. This organic material showed an amorphous behavior with a T_g of 70 °C. The absorption and fluorescence properties of the polymer were investigated. The HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. The PAnS thin film exhibits an optical gap of 2.56 eV and emits in orange region. The fluorescence quantum efficiency in dilute solution of PAnS was of 66%. A PAnS-based single-layer diode has been fabricated and shows relatively low turn-on voltage of 4.8 V.     

Synthesis of PbS/poly (vinyl-pyrrolidone) nanocomposite

A simple solution growth method for synthesis of nanocomposite of PbS nanoparticles in poly(vinyl-pyrrolidone) (PVP) polymer is described. The nanocomposite is prepared from methanolic solution of lead acetate (PbAc), thiourea (TU) and PVP at room temperature (∼27 °C). Optical absorption spectrum of PbS/PVP nanocomposite solution shows strong absorption from 300 to 650 nm with significant bands at 400 and 590 nm which is characteristic of nanoscale PbS. Spin-coated nanocomposite films on glass have an absorption edge at ∼650 nm with band gap of 2.55 eV. Fourier transform infrared (FTIR) spectroscopy of PbS/PVP nanocomposite and PVP shows strong chemical bond between PbS nanoparticles and host PVP polymer. The transmission electron microscope (TEM) images reveal that 5-10 nm PbS particles are evenly embedded in PVP polymer. The formation of PbS is confirmed by selective area electron diffraction (SAED) of a typical nanoparticle.     

CdSe thin films: morphological, optoelectronic and photoelectrochemical studies

Polycrystalline cadmium selenide (CdSe) thin films have been synthesized at room temperature by using chemical bath deposition method. The synthesized films were characterized by using X-ray diffraction (XRD), optical absorbance, electrical conductivity, scanning electron microscope, energy dispersive X-ray analysis, photoluminescence and photoelectrochemical (PEC) techniques. The film of 0.84 μm thickness, deposited on glass substrate showed uniform spherical morphology with an optical band gap of 1.99 eV. The XRD analysis confirmed presence of cubic structure. Scanning electron micrograph shows a typical spherical ball like morphology with large surface area, which is useful for absorption of large solar radiation. The conductivity measurements showed n type semiconducting nature of the film. A PEC cell device fabricated using ‘as deposited’ CdSe film as anode showed a stable conversion efficiency of 0.7 %.     

Electrical stability of polyimide siloxane films for interlayer dielectrics in multilevel interconnections

Electrical stability of a polyimide siloxane (PSI) film for ultra-large scale integrated circuit (ULSI) multilevel interconnections is studied. The PSI films, modified by p-aminophenyltrimethoxysilane (APTMS), are designed to have three-dimensional polymer structures through Si–O bonds. It has been revealed that the PSI films are more stable in electrical properties at higher temperatures than 150°C, as compared to the conventional polyimide (PI) films. The electrical conduction mechanism study for the PSI films has revealed that Schottky emission is dominant. Barrier height φ_B obtained from the electrical property for the PSI film was 0.460 eV in the temperatures ranging from 25–250°C. On the other hand, barrier height of 0.422 eV at lower temperatures than 150°C and activation energy of 1.09 eV at higher temperatures than 150°C were obtained for the conventional PI film. The difference in polymer structure is very sensitive to the electrical conduction at high temperature, due to sodium ion migration. The ideal band diagrams of metal-insulator-semiconductor (MIS) structures were also discussed. The optical band gaps for PSI and conventional PI films were 3.320 eV and 3.228 eV, respectively. This result suggests that the band gap of PI films can be enlarged by modification with Si–O components. The differential barrier height between the PSI and conventional PI films is 0.038 eV, and is close to the difference in half of optical band gaps (0.046 eV).     

低带隙共轭聚合物的合成及光学性质

在钯催化剂的作用下,通过4,7-二溴[2,1,3]苯并噻二唑与2,5-二乙炔基-3-辛基噻吩的偶联反应,合成了一种新的共轭高分子PTE-BT.采用紫外可见吸收光谱及荧光光谱对其光学性质进行了研究.紫外可见吸收谱结果表明,PTE-BT的固体膜光学带隙为1.86 ev;TiO2/PTE-BT共混固体膜的荧光发射谱结果表明,电子供体PTE-BT分子与电子受体TiO2分子间存在有效的电子转移.     

Synthesis and optical properties of nanocrystalline V-doped ZnO powders

This paper reports the synthesis and optical properties of nanocrystalline powders of V-doped ZnO (i.e. Zn_0.95V_0.05O, Zn_0.90V_0.10O, and Zn_0.85V_0.15O) by a simple sol–gel method using metal acetylacetonates of Zn and V and poly(vinyl alcohol) as precursors. Structure of the prepared samples was studied by X-ray diffraction, FTIR spectroscopy, and selected-area electron diffraction (SAED) analysis. The morphology of the powders revealed by SEM and TEM was affected by the amount of V, causing the formations of both nanoparticles and nanorods in the Zn_0.95V_0.05O sample, nanorods in the Zn_0.90V_0.10O sample, and nanoparticles in the Zn_0.85V_0.15O sample. The optical properties of the samples were investigated by measuring the UV–VIS absorbance and photoluminescence spectra at room temperature. All the samples exhibited UV absorption at below 400 nm (3.10 eV) with a well-defined absorbance peak at around 364 nm (3.41 eV) and 288 nm (4.31 eV). The band gap of the V-doped samples shows a decrease with increasing V concentration. The photoluminescence spectra of all the samples showed a strong UV emission band at 2.98 eV, a weak blue band at 2.82 eV, a week blue–green band at 2.56 eV, and a weak green band at 2.34 eV, which indicated their high structural and optical quality.     

Electro-optical properties of poly[di(2-thiophenyl)carborane] and its opto-electronic application

Electrochemical and optical properties of a hybrid carborane based polymer called poly(di(2-thiophenyl)carborane) (P1) obtained electrochemically were reported as well as its electrochromic device application. Thiophene donor units and m-carborane acceptor unit were combined under the same umbrella via donor–acceptor–donor approach to obtain di(2-thiophenyl)carborane (1). Contrary to the literature, extreme conditions like highly dried solvent or inert atmosphere were not used for polymerization and characterization. Polymer P1 has an ambipolar character since it exhibited a reversible oxidation peak at a half wave potential (E_1/2) of 1.08 V and a quasi reversible reduction peak at E_1/2 = −1.82 V vs. Ag/AgCl. The polymer film has an optical band gap of 1.95 eV with a maximum absorption band centered at 488 nm. Also, it exhibited multicolor electrochromic behavior between its reduced and oxidized states changing from dark orange to light blue. Furthermore, the electrochromic device prepared based on P1 film was stable and robust.     

Synthesis and photovoltaic properties of new conjugated polymers based on benzo[1,2-b:4,5-b']dithiophene

New conjugated polymers based on benzo[1,2-b:4,5-b']dithiophene, poly(benzo[1,2-b:4,5-b'] dithiophene-alt-bithiophene) (PBT-2T) and poly(benzo[1,2-b:4,5-b']dithiophene-alt-terthiophene) (PBT-3T), have been synthesized via the Stille coupling reaction and their optical and electrochemical properties were characterized by UV-vis, photoluminescence (PL) and cyclic voltammetry (CV) measurements. Compared to PBT-2T, PBT-3T film showed clearly red-shifted UV-visible absorption and PL spectra with maxima at 511 and 653 nm, respectively. Especially, PBT-3T containing terthiophene showed very small optical band gap of 1.65 eV. The PBT-2T and PBT-3T showed the power conversion efficiencies of 0.25% and 0.34%, respectively, under AM 1.5 (100 m/cm2).