New low band gap 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c `]bis1,2,5]thiadiazole based conjugated polymers for organic photovoltaics

Two new low band gap D-A structured conjugated polymers, PBDTTBI and PBDTBBT, based on 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole acceptor units with benzo1,2-b; 3,4-b']dithiophene as a donor unit have been designed and synthesized via a Stille coupling reaction. The incorporation of the benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole unit into PBDTBBT has significantly altered the optical and electrochemical properties of the polymer. The optical band gap estimated from the onset absorption edge is similar to 1.88 eV and similar to 1.1 eV, respectively for PBDTTBI and PBDTBBT. It is observed that PBDTBBT exhibited a deeper HOMO energy level (similar to 4.06 eV) with strong intramolecular charge transfer interactions. Bulk heterojunction solar cells fabricated with a configuration of ITO/PEDOT: PSS/PBDTBBT: PC71BM/Al exhibited a best power conversion efficiency of 0.67%, with a short circuit current density of 4.9 mA cm(-2), an open-circuit voltage of 0.54 V and a fill factor of 25%.

Efficient charge transfer and field-induced tunneling transport in hybrid composite device of organic semiconductor and cadmium telluride quantum dots

Temperature and photo-dependent current-voltage characteristics are investigated in thin film devices of a hybrid-composite comprising of organic semiconductor poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) and cadmium telluride quantum dots (CdTe QDs). A detailed study of the charge injection mechanism in ITO/PEDOT: PSS-CdTe QDs/Al device exhibits a transition from direct tunneling to Fowler-Nordheim tunneling with increasing electric field due to formation of high barrier at the QD interface. In addition, the hybrid-composite exhibits a huge photoluminescence quenching compared to aboriginal CdTe QDs and high increment in photoconductivity (similar to 400%), which is attributed to the charge transfer phenomena. The effective barrier height (Phi(B) approximate to 0.68 eV) is estimated from the transition voltage and the possible origin of its variation with temperature and photo-illumination is discussed. (C) 2015 AIP Publishing LLC.

A highly conductive and transparent solution processed AZO/MWCNT nanocomposite

A solution processed aluminum-doped zinc oxide (AZO)/multi-walled carbon nanotube (MWCNT) nanocomposite thin film has been developed offering simultaneously high optical transparency and low electrical resistivity, with a conductivity figure of merit (σDC/σopt) of ~75-better than PEDOT:PSS and many graphene derivatives. The reduction in sheet resistance of thin films of pristine MWCNTs is attributed to an increase in the conduction pathways within the sol-gel derived AZO matrix and reduced inter-MWCNT contact resistance. Films have been extensively characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffractometry (XRD), photoluminescence (PL), and ultraviolet-visible (UV-vis) spectroscopy. © 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Optical investigations of the effect of solvent and thermal annealing on the optoelectronic properties of Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) films

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most promising conducting polymers that can be used as transparent electrode or as buffer layer for organic electronic devices. However, when used as an electrode, its conductivity has to be optimized either by the addition of solvents or by post-deposition processing. In this work, we investigate the effect of the addition of the polar solvent dimethylsulfoxide (DMSO) to an aqueous PEDOT:PSS solution on its optical and electrical properties by the implementation of the Drude model for the analysis of the measured pseudo-dielectric function by Spectroscopic Ellipsometry from the near infrared to the visible-far ultraviolet spectral range. The results show that the addition of DMSO increases significantly the film conductivity, which reaches a maximum value at an optimum DMSO concentration as it has confirmed by experimentally measured conductivity values. The post-deposition thermal annealing has been found to have a smaller effect on the film conductivity. © 2013 Elsevier B.V.

Effect of process parameters on the morphology and nanostructure of roll-to-roll printed P3HT:PCBM thin films for organic photovoltaics

Roll-to-roll (R2R) gravure exhibits significant advantages such as high precision and throughput for the printing of photoactive and conductive materials and the fabrication of flexible organic electronics such as organic photovoltaics (OPVs). Since the photoactive layer is the core of the OPV, it is important to investigate and finally control the process parameters and mechanisms that define the film morphology in a R2R process. The scope of this work is to study the effect of the R2R gravure printing and drying process on the nanomorphology and nanostructure of the photoactive P3HT:PCBM thin films printed on PEDOT:PSS electrodes towards the fabrication of indium tin oxide (ITO)-free flexible OPVs. In order to achieve this, P3HT:PCBM blends of different concentration were R2R printed under various speeds on the PEDOT:PSS layers. Due to the limited drying time during the rolling, an amount of solvent remains in the P3HT:PCBM films and the slow-drying process takes place which leads to the vertical and lateral phase separation, according to the Spectroscopic Ellipsometry and Atomic Force Microscopy analysis. The enhanced slow-drying leads to stronger phase separation, larger P3HT crystallites according to the Grazing Incidence X-Ray Diffraction data and to weaker mechanical response as it was shown by the nanoindentation creep. However, in the surface of the films the P3HT crystallization is controlled by the impinged hot air during the drying, where the more the drying time the larger the surface P3HT crystallites. The integration of the printed P3HT:PCBM and PEDOT:PSS layers in an OPV device underlined the feasibility of fabricating ITO-free flexible OPVs by R2R gravure processes. © 2013 Elsevier B.V.

Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.

Performance of hybrid buffer Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) layers doped with plasmonic silver nanoparticles

We compare the performance of a typical hole transport layer for organic photovoltaics (OPVs), Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) thin film with a series of PEDOT:PSS layers doped with silver (Ag) nanoparticles (NPs) of various size distributions. These hybrid layers have attracted great attention as buffer layers in plasmonic OPVs, although there is no report up to date on their isolated performance. In the present study we prepared a series of PEDOT:PSS layers sandwiched between indium tin oxide (ITO) and gold (Au) electrodes. Ag NPs were deposited on top of the ITO by electron beam evaporation followed by spin coating of PEDOT:PSS. Electrical characterization performed in the dark showed linear resistive behavior for all the samples; lower resistance was observed for the hybrid ones. It was found that the resistivity of the samples decreases with increasing the particle's size. A substantial increase of the electric field between the ITO and the Au electrodes was seen through the formation of current paths through the Ag NPs. A striking observation is the slight increase in the slope of the current density versus voltage curves when measured under illumination for the case of the plasmonic layers, indicating that changes in the electric field in the vicinity of the NP due to plasmonic excitation is a non-vanishing factor. © 2014 Published by Elsevier B.V. All rights reserved.

Synthesis of MDMO-PPV capped PbS quantum dots and their application to solar cells

Poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) capped PbS quantum dots about 3-6 nm in diameter were synthesized with a novel method. Unlike the synthesis of oleic acid capped PbS quantum dots, the reactions were carried out in solution at room temperature, with the presence of a capping ligand species, MDMO-PPV. The quantum dots were used to fabricate bulk heterojunction solar cells with an indium tin oxide (ITO)/polyethylenedioxythiophene/polystyrenesulphonate (PEDOT: PSS)/MDMO-PPV: PbS/Al structure. Current density-voltage characterization of the devices showed that after the addition of the MDMO-PPV capped PbS quantum dots to MDMO-PPV film, the performance was dramatically improved compared with pristine MDMO-PPV solar cells. (C) 2008 Elsevier Ltd. All rights reserved.

The application of SnS nanoparticles to bulk heterojunction solar cells

Tin mono-sulphide (SnS) nanoparticles were synthesized by a facile method. Reactions producing narrow size distribution SnS nanoparticles with the diameter of 5.0-10 nm were carried out in an ethylene glycol solution at 150 degrees C for 24 h. Bulk heterojunction solar cells with the structure of indium tin oxide (ITO)/polyethylenedioxythiophene polystyrenesulphonate (PEDOT PSS)/SnS polymer/Al were fabricated by blending the nanoparticles with a conjugated polymer to form the active layer for the first time. Current density-voltage characterization of the devices showed that due to the addition of SnS nanoparticles to the polymer film, the device performance can be dramatically improved, compared with that of the pristine polymer solar cells. (c) 2009 Published by Elsevier B.V.

The synthesis of MDMO-PPV capped PbS nanorods and their application in solar cells

Poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) capped PbS nanorods about 100 nm in diameter and 400 nm in length were synthesized via a hydrothermal route in toluene and dimethylsulfoxide solution. By blending the PbS nanorods with the MDMO-PPV as the active layer, bulk heterojunction solar cells with an indium tin oxide (ITO)/polyethylenedioxythiophene/polystyrenesulphonate (PEDOT PSS)/MDMO-PPV PbS nanorods/Al structure were fabricated in a N-2 filled glove box, Current density-voltage characterization of the devices showed that the solar cells with PbS nanorods hybrid with MDMO-PPV as active layer were better in performance than the devices with the polymer only. (C) 2009 Elsevier B.V. All rights reserved.

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly [2- methoxy-5 - (3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electrolummescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection. (c) 2007 Elsevier B.V. All rights reserved.

有机近红外电致变色器件

光通讯近年来发展迅速，正在从元件向集成发展，迫切需要利于集成的元件。主要的一些光学元件如激光器、放大器等均采用无机材料，连接和集成存在困难。发展易于集成的有机光学元件是目前该领域研发的一个热点。电致变色是一个古老的题目，一般都在可见区，而光通讯波长主要是1300和1550nm，是近红外区。在近红外区的工作刚刚开始，．用于光衰减器的研究已有报道，但还没有达到实际要求，寻找新型的电致变色材料及其适合这些材料的新的器件构型是目前研究的重点。本文研究了三种新的有机近红外电致变色材料及其器件：PEDOT:PSS、Ru星状化合物和酞警噜。本文通过电化学、吸收光谱、X射线衍射、AFM等实验方法和手段表征了样品的本体性质、近红外电致变色，性质和器件性能。结果如下：本论文首先研究了PEDOT:PSS的近红外电致变色性质。实验结果首次表明通过掺杂如Liclo4的电解质可以提高近红外电致变色器件的性能。通过掺杂，褪色时间从30秒缩短到2.8秒，着色时间从9.2秒缩短到2.7秒，变色效率从105cm2／C提高到3llcm2／C。掺杂后薄膜离子导电率提高是器件性能改善的原因。另外还制备了基于不同厚度的PEDOT：PSS薄膜的器件，发现对于一定掺杂浓度有一个最佳的厚度，在这个厚度下器件有较大的调制能力和较小的透过损失。本论文第二部分研究Ru星状化合物。通过对基于Ru星状化合物溶液的动力学的研究，证明了调制能力与溶液浓度和外加电压的关系。之后研究开发了有新构型的近红外电致变色器件，以Ru（II，II）态化合物溶液代替其交联薄膜和电解质层来形成固液型器件，同时改善了氧化钨的制备方法。将器件对1550nm光的调制能力从文献报道的2dB提高到16dB。本论文还首次报道了酞警噜的近红外电致变色性质，发现它既可以作为阳极电致变色材料也可以作为阴极电致变色材料。酞普噜的溶液和薄膜均可用于制备电致变色器件，器件的响应速度分别为23秒和1秒。但因为中性态酞警噜对1300nm和1550nm的光吸收较小，器件的调制能力也较小（-0.3dB）。 论文的最后部分详细阐述了有机光电器件表征系统的搭建及测量方法，包括电调制光的电致变色器件测试系统、光转换为电的有机光电二极管或太阳能电池等光电器件测试系统和电转换为光的有机电致发光二极管的器件测试系统。本论文的结果证明采用新构型可以提高近红外电致变色器件的性能；通过掺杂可以缩短电致变色器件的响应时间和提高其变色效率；同时还首次报道了酞瞥噜的近红外电致变色性质。

Novel White Electroluminescent Single Polymer Derived from Fluorene and Quinacridone

A novel series of white light emitting single polymers are prepared by incorporating low contents of quinacridone into the main chain of polyfluorene. This is the first report of quinacridone-containing conjugated polymer. Single layer devices (ITO/PEDOT:PSS/polymer/Ca/Al) are fabricated with these polymers. Energy transfer from fluorene segments to quinacridone unit is observed. Moreover, in the EL process, quinacridone unit can trap electrons and cannot trap holes from fluorene segments.

Performance Enhancement of Polymer Light-Emitting Diodes by Using Ultrathin Fluorinated Polyimide Modifying the Surface of Poly(3,4-ethylene dioxythiophene):Poly(styrenesulfonate)

Herein, an insulating fluorinated polyimide (F-PI) is utilized as an ultrathin buffer layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in polymer light-emitting diodes to enhance the device performance. The selective solubility of F-PI in common solvents avoids typical intermixing interfacial problems during the sequential multilayer spin-coating process. Compared to the control device, the F-PI modification causes the luminous and power efficiencies of the devices to be increased by a factor of 1.1 and 4.7, respectively, along with almost 3-fold device lifetime enhancement. Photovoltaic measurement, single-hole devices, and X-ray photoelectron spectroscopy, are utilized to investigate the underlying, mechanisms, and it is found that the hole injection barrier is lowered owing to the interactions between the PEDOT:PSS and F-PI. The F-PI modified PEDOT:PSS layer demonstrates step-up ionization potential profiles from the intrinsic bulk PEDOT:PSS side toward the F-PI-modified PEDOT:PSS surface, which facilitate the hole injection.

Synthesis and chain-length dependent properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s (OFVs) with fluorene units up to 11 has been synthesized following a divergent approach. Chain length was found to affect not only photophysical properties but also thermal properties. Absorption and photoluminescence spectra are red-shifted with increasing chain length. The effective conjugated length has been extrapolated to be as long as 19 fluorene vinylene units, indicative of a well-conjugated system. With the number of fluorene units > 5, the oligomers exhibit nematic mesomorphism. Glass transition temperature (T-g) and clearing point temperature (T-c) increase with increasing molecular length and with those of OFV11 up to 71 and 230 degrees C, respectively. The oligomers can form uniform films by solution casting for fabrication of light-emitting diodes. With a device structure of ITO/ PEDOT:PSS/OFV11/Ca/Al, a current efficiency of 0.8 cd.A(-1) at a brightness of 1300 cd.m(-2) along with a maximum brightness of 2690 cd.m(-2) have been realized. This performance is notably superior to that of the corresponding polymer.