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1.
    
The photophysical properties of blends of fluorene copolymer and the fullerene derivative PCBM are analyzed with a particular attention to photovoltaic applications. The properties of the blends are determined by the relative alignment of the HOMO energy levels. In the blend where the HOMO levels of the copolymer and the fullerene are aligned there is not signature of charge stabilization and photovoltaic effect. While in the blend where there is an offset between the HOMO levels the charge stabilization is accompanied by good photovoltaic performances. The photoluminescence spectrum of the latter blend is characterized by the appearance of a new peak at low energy with a lifetime of a few ns that red‐shifts with the increase of the PCBM percentage. The feature is attributed to the emission from a charge‐transfer exciton that is red‐shifted by the change of dielectric constant of the medium.  相似文献   

2.
    
A highly elastic and stretchable conductive polymer material resulted from blending the conductive polymer poly(3,4‐ethylenedioxythiophene):p‐tosylate and an aliphatic polyurethane elastomer. The blend inherited advantageous properties from its constituents, namely high conductivity of 120 S cm–1 from its conductive polymer component, and elastomeric mechanical properties resembling those of the polyurethane, including good adhesion to various substrates. Stretching of the blend material by up to 50 % resulted in increased conductivity, while subsequent relaxation to the unstretched state caused a decrease of conductivity compared to the pristine blend. These initial changes in conductivity were reproducible on further cycling between 50 % stretching and the unstretched state for at least 10 cycles. Stretching beyond 50 % resulted in decreasing conductivity of the blend but with substantial conductivity remaining even when stretched by 200 %. Optical, mechanical, and thermal properties of the blend, as well as high resolution electron microscopy of bulk cross‐sections, suggest that the system is a single phase and not two separate phases. Ageing experiments indicate that the material retains substantial conductivity for at least a few years at room temperature.  相似文献   

3.
    
Perpendicularly arrayed and size‐controlled nanocylinders have been prepared by simply blending an asymmetric polystyrene‐block‐polyisoprene‐block‐polystyrene triblock copolymer with polystyrene (the minority component) homopolymers of different molecular weights. The preference for perpendicular orientation or hexagonal ordering of the nanocylinders over a large area in the asymmetric block copolymer can be controlled by adjusting the molecular weight of the blended homopolymer, and the perfection of hexagonal ordering of the perpendicular cylinders can be tuned by using a substrate whose surface tension is much different from that of the majority component of the block copolymer. Such highly controlled nanostructured block‐copolymer materials, which have been obtained by a simple method independent of film thickness and interfacial tension between the blocks and the substrates, have wide‐ranging commercial potential, e.g., for use in membranes and nanotemplates with size‐tunable pores, bandgap‐controlled photonic crystals, and other nanotechnological fields demanding a specific nanosize and nanomorphology.  相似文献   

4.
Polymer solar cells based on poly (2-methoxy-5-(2′-ethyl-hexyloxy)-1, 4-phenylene vinylene) (MEH-PPV):1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6)C61(PCBM):3, 10-di(trifluoromethane) triphenodioxazine (TFTD) was fabricated using spin coating technology. The absorption spectra of MEH-PPV: PCBM: TFTD film coated from chlorobenzene solution was broadened and showed higher intensity compared with that of the pure MEH-PPV. The TFTD acting as electron acceptors in combination with PCBM induced the photoluminescence (PL) quenching of MEH-PPV, which were associated with the photoinduced charge transfer characteristics of composite film. Further, a photovoltaic conversion efficiency up to 1.03% under 16.7 mW/cm2 white light illumination was achieved in the MEH-PPV: PCBM: TFTD system.  相似文献   

5.
    
The influence of the solvent on the morphology and performance of polymer solar cells is investigated in devices based on blends of the polyfluorene copolymer, poly(2,7‐(9,9‐dioctyl‐fluorene)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)), and [6,6]‐phenyl‐C61‐butyric acid methyl ester. The blends are spin‐coated from chloroform or from chloroform mixed with small amounts of xylene, toluene, or chlorobenzene. The devices are characterized under monochromatic light and solar illumination AM1.5 (AM: air mass). An enhancement of the photocurrent density is observed in diodes made from chloroform mixed with chlorobenzene, and reduced photocurrent density is observed in diodes made from chloroform mixed with xylene or toluene, compared to diodes made from neat chloroform. The open‐circuit voltages are almost the same in all diodes. The surfaces of the active layers are imaged using atomic force microscopy. Height images indicate that a finer and more uniform distribution of domains corresponds to the diodes with enhanced photocurrent that are made from chloroform mixed with chlorobenzene, while a structure with larger domains is associated with the lower photocurrents in the diodes made from chloroform mixed with xylene or toluene. The influence of the morphology on the excited‐state dynamics and charge generation is investigated using time‐resolved spectroscopy. Fast formation of bound charge pairs followed by their conversion into free charge carriers is resolved, and excitation‐intensity‐dependent non‐geminate recombination of free charges is observed. A significant enhancement in free‐charge‐carrier generation is observed on introducing chlorobenzene into chloroform. Imaging photocurrent generation from the solar cells with a light‐pulse technique shows an inhomogeneous photocurrent distribution, which is related to the undulations in the thickness of the active layer. Thicker parts of the diodes yield higher photocurrent values.  相似文献   

6.
    
A biodegradable, immiscible poly(butylenes adipate‐co‐butylenes terephthalate) [P(BA‐co‐BT)]/poly(ethylene oxide) (PEO) polymer blend film with compositional gradient in the film‐thickness direction has been successfully prepared in the presence of a low‐molecular‐weight compound 4,4′‐thiodiphenal (TDP), which is used as a miscibility‐enhancing agent. The miscibilities of the P(BA‐co‐BT)/PEO/TDP ternary blend films and the P(BA‐co‐BT)/PEO/TDP gradient film were investigated by differential scanning calorimetry (DSC). The compositional gradient structure of the P(BA‐co‐BT)/PEO/TDP (46/46/8 w/w/w) film has been confirmed by microscopic mapping measurement of Fourier‐transform infrared spectra and dynamic mechanical thermal analysis. We have developed a new strategy for generating gradient‐phase structures in immiscible polymer‐blend systems by homogenization, i.e., adding a third agent that can enhance the miscibility of the two immiscible polymers through simultaneous formation of hydrogen bonds with two component polymers.  相似文献   

7.
    
The photophysical properties, i.e., the fluorescence and phosphorescence of a series of blue light‐emitting poly(ladder‐type phenylene)s have been investigated employing continuous‐wave (cw) and time‐resolved photoluminescence (PL) spectroscopy in solid state and dilute solution. The chemically well‐defined polymers vary from two to five bridged phenyl‐rings per monomer unit bearing aryl‐ or alkyl‐substitution at the bridge‐head carbon atoms. It has been found that the fluorescence energy of the polymers and of the corresponding monomers deviates from a simple 1/N dependence, if the number N of bridged‐phenylene rings is increased beyond a certain limit. Time‐resolved fluorescence spectroscopy on thin films showed that apart from the blue fluorescence of the polymers an additional lower energy emission feature exists, which cannot be assigned to keto‐defects and which seems to be an inherent solid state property of this class of materials. Delayed time‐resolved photoluminescence spectroscopy allowed the detection of phosphorescence energies and lifetimes for all investigated polymers. Photoinduced absorption spectroscopy on thin films showed that the triplet‐triplet absorption red‐shifts with increasing monomer length but reaches a constant value for polymers with N ≥ 4. Amplification of light via amplified spontaneous emission (ASE) from thin film slab waveguide structures could be demonstrated for all ladder‐type polymers but the onset threshold value for ASE varies significantly with the polymer structure.  相似文献   

8.
    
In this paper a novel technique for the production of aluminosilicate microtubes, which are shown to act as optical cylindrical microresonators, is described. The free‐standing microtubes are fabricated by using vacuum‐assisted wetting and filtration of silica gel through a microchannel glass matrix. The microtubes are studied using scanning electron microscopy, micro‐photoluminescence spectroscopy, and fluorescence lifetime imaging confocal microscopy. In the emission spectra of the microresonators we find very narrow periodic peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors up to 3200. A strong enhancement in photoluminescence decay rates at high excitation power demonstrates the occurrence of amplified spontaneous emission from a single microtube. These microtubes show a large evanescent field extending many micrometers beyond the tube radius. Applications for these novel microresonators will be in the areas of microlasers and microsensors and quantum information processing.  相似文献   

9.
Photoluminescence and photovoltaic properties of P3OT:%CdSe nanocomposite films are investigated as a function of the mass concentration (wt%) of the CdSe nanoparticles (NPs) incorporated in the films. The incorporation of CdSe NPs produces a quenching of the photoluminescence and improves the performance of the nanocomposite solar cells. These effects are explained in terms of exciton dissociation and charge separation occurring at P3OT/CdSe interfaces within the Förster formalism, involving non-radiative energy transfer from the donor (P3OT) to the acceptor (CdSe NPs). An exciton quenching rate constant of 1.4×10−10 cm3 s−1 is determined using the Stern–Volmer equation. In addition, scanning electron microscopy (SEM) images reveal that surface morphology is changed by CdSe NPs incorporation, in agreement with FTIR spectra. The current density–voltage (J–V) characteristics of ITO/P3OT:%CdSe/Al photovoltaic cells performed for different CdSe concentrations are also reported and indicate a significant improvement of the photovoltaic parameters cells, particularly, the conversion efficiency becomes 20 times greater than that of the cell based on pure polymer.  相似文献   

10.
    
Here, studies on the evolution of photophysics and device performance with annealing of blends of poly(3‐hexylthiophene) with the two polyfluorene copolymers poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2′′‐diyl) (F8TBT) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) are reported. In blends with F8TBT, P3HT is found to reorganize at low annealing temperatures (100 °C or below), evidenced by a redshift of both absorption and photoluminescence (PL), and by a decrease in PL lifetime. Annealing to 140 °C, however, is found to optimize device performance, accompanied by an increase in PL efficiency and lifetime. Grazing‐incidence small‐angle X‐ray scattering is also performed to study the evolution in film nanomorphology with annealing, with the 140 °C‐annealed film showing enhanced phase separation. It is concluded that reorganization of P3HT alone is not sufficient to optimize device performance but must also be accompanied by a coarsening of the morphology to promote charge separation. The shape of the photocurrent action spectra of P3HT:F8TBT devices is also studied, aided by optical modeling of the absorption spectrum of the blend in a device structure. Changes in the shape of the photocurrent action spectra with annealing are observed, and these are attributed to changes in the relative contribution of each polymer to photocurrent as morphology and polymer conformation evolve. In particular, in as‐spun films from xylene, photocurrent is preferentially generated from ordered P3HT segments attributed to the increased charge separation efficiency in ordered P3HT compared to disordered P3HT. For optimized devices, photocurrent is efficiently generated from both P3HT and F8TBT. In contrast to blends with F8TBT, P3HT is only found to reorganize in blends with F8BT at annealing temperatures of over 200 °C. The low efficiency of the P3HT:F8BT system can then be attributed to poor charge generation and separation efficiencies that result from the failure of P3HT to reorganize.  相似文献   

11.
    
We have identified viable operating principles for the modulation of optical signals under the influence of optical stimulations. They are based on the overlap between the emission bands of a fluorescent compound and the absorption bands of one of the two forms of a bistable photochromic switch. Under these conditions, the photoinduced interconversion of the two states of the photochrome modulates efficiently the emission intensity of the fluorophore. We have implemented this mechanism for intermolecular fluorescence modulation with multilayer structures. They consist of two quartz plates sandwiching two overlapping polymer layers. One of the polymers is doped with a fluorescent benzofurazan. The other contains a photochromic spiropyran. The multilayer assembly is operated with two light sources. One of them is centered at the excitation wavelength of the fluorophore, where neither of the two states of the photochrome absorbs. The other light source is switched between ultraviolet and visible wavelengths to induce the interconversion between the two states of the photochrome. The light emitted by the fluorescent component has to propagate through the photochromic layer before reaching a detector. It can do so efficiently for only one of the two states of the photochrome. It follows that a measurement of the light intensity reaching the detector can read the state of the photochromic switch, which in turn is written and erased with optical stimulations. Thus, our strategy for all‐optical processing can be used to store and retrieve binary digits, as well as to implement optical inversion, with the aid of engineered molecule‐based components.  相似文献   

12.
The phase segregation in P3HT:PCBM blend films has been investigated from an experimental and theoretical viewpoint. Optical microscopy, atomic force microscopy, scanning electron microscopy and X-ray diffraction show that thermal annealing of P3HT:PCBM blend films leads to the formation of PCBM aggregates. These aggregates are composed of dense randomly packed ∼50 nm PCBM crystallites with an overall aggregate density of ∼0.85 g cm−3. By applying the critical radius of nucleation for PCBM and the Stokes-Einstein equation for mobility of PCBM in a P3HT matrix, a model is developed which explains the formation of both crystallites and aggregates.  相似文献   

13.
    
We develop a universal method for spray-deposition of polymeric semiconductor blends, based on blends of polyfluorenes (F8TBT), polythiophenes (P3HT) and fullerenes (PCBM), as suitable for large areas. A multi-faceted characterisation approach, studying photoluminescence quenching, together with atomic force and optical microscopy, illustrates favourable results in terms of layer thickness, uniformity, and mesoscale morphology. With key engineering tolerances in mind, thermal (melt) and solvent-vapour annealing are investigated as post-processing methods, for improving the planarity of craterform layers and blend photophysical characteristics.  相似文献   

14.
    
In organic bulk heterojunction solar cells (oBHJ) the blend morphology in combination with the charge transport properties of the individual components controls the extracted photocurrent. The organic field‐effect transistor (OFET) has been proved as a powerful instrument to evaluate the unipolar carrier transport properties in a wide range of cases. In our work we extend the OFET concept to the evaluation of the bipolar transport properties in polymer‐fullerenes blends and propose a method to improve the accuracy of the evaluation. The method is based on capacitance–voltage (C–V) measurements on MOS structures prepared on the same blends and delivers complementary information on the bulk heterojunction to the one obtained with FETs. The relevance for photovoltaic applications is investigated through the correlation between the current–voltage behavior of solar cells and the bipolar mobility for composites with varying polymer molecular weight and processed from different solvents. In particular the transport features of solar cells produced from o‐Xylene (oX), a non chlorinated solvent more suitable to production requirements, have been compared to the one of devices cast from Chlorobenzene (CB) solution. For the P3HT‐PCBM blend a consistent correlation between the mobility and the electrical fill factor and power performance was found. A significant asymmetry in the bipolar carrier mobility, together with low electron mobility dependent on the Mw value, affects the performances of thick o‐Xylene cast devices. In the case of devices processed from Chlorobenzene the slower carrier has higher mobility and the small electrical losses detected are eventually more related to the formation of space‐charge and eventually to surface recombination. This results in an efficient charge collection that is almost thickness independent. We report a dependence of the slow‐carrier type (electrons or holes) and their mobility on the specific combination of molecular weight and solvent. The mobility data and the solar cell performance coherently fit to the prediction of a device model only based on the drift of carriers under the built‐in electric field originated in the donor‐acceptor oBHJ.  相似文献   

15.
    
A new ordered structure of the C60 derivative PCBM ([6‐6]‐phenyl C61‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.  相似文献   

16.
    
Blends of nanocrystalline zinc oxide nanoparticles (nc‐ZnO) and regioregular poly(3‐hexylthiophene) (P3HT) processed from solution have been used to construct hybrid polymer–metal oxide bulk‐heterojunction solar cells. Thermal annealing of the spin‐cast films significantly improves the solar‐energy conversion efficiency of these hybrid solar cells to ～ 0.9 %. Photoluminescence and photoinduced absorption spectroscopy demonstrate that charge‐carrier generation is not quantitative, because a fraction of P3HT appears not to be in contact with or in close proximity to ZnO. The coarse morphology of the films, also identified by tapping‐mode atomic force microscopy, likely limits the device performance.  相似文献   

17.
    
A new ordered structure of the C60 derivative PCBM is obtained in thin films based on the blend PCBM:P3HT, as detailed by Swinnen, Manca, and co‐workers on p. 760. Needlelike crystalline PCBM structures, whose dimensions and spatial distribution ca be tuned by adjusting the blend ratio and annealing conditions, are formed. In typical solar‐cell applications of these blended films, these results indicate that during long‐term operation under normal conditions (50–70 °C) morphology changes and a decrease in cell performance could occur. A new ordered structure of the C60 derivative PCBM ([6‐6]‐phenyl C61‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.  相似文献   

18.
    
Light‐induced generation of charges into an electron acceptor–donor phase‐segregated blend is studied. The blend is made of highly ordered nanoscopic crystals of 3″‐methyl‐4″‐hexyl‐2,2′:5′,2″:5″,2?:5?,2″″‐quinquethiophene‐1″,1″‐dioxide embedded into a regioregular poly(3‐hexylthiophene) matrix, acting as acceptor and donor materials, respectively. Kelvin probe force microscopy investigations reveal a tendency for the acceptor nanocrystals to capture the generated electrons whereas the donor matrix becomes more positively charged. The presence of particular positively charged defects, i.e., nanocrystals, is also observed within the film. The charging and discharging of both materials is studied in real time, as well as the effect of different acceptor–donor ratios. Upon prolonged thermal annealing at high temperatures the chemical structure of the blend is altered, leading to the disappearance of charge separation upon light irradiation. The obtained results allow a better understanding of the correlation between the nanoscopic structure of the photoactive material and solar‐cell performance.  相似文献   

19.
    
The function of organic solar cells is based upon charge photogeneration at donor/acceptor heterojunctions. In this paper, the origin of the improvement in short circuit current of poly(3‐hexylthiophene)/6,6‐phenyl C61‐butyric acid methyl ester (P3HT/PCBM) solar cells with thermal annealing is examined. Transient absorption spectroscopy is employed to demonstrate that thermal annealing results in an approximate two‐fold increase in the yield of dissociated charges. The enhanced charge generation is correlated with a decrease in P3HT's ionization potential upon thermal annealing. These observations are in excellent quantitative agreement with a model in which efficient dissociation of the bound radical pair into free charges is dependent upon the bound radical state being thermally hot when initially generated, enabling it to overcome its coulombic binding energy. These observations provide strong evidence that the lowest unoccupied molecular orbital (LUMO) level offset of annealed P3HT/PCBM blends may be only just sufficient to drive efficient charge generation in polythiophene‐based solar cells. This has important implications for current strategies to optimize organic photovoltaic device performance based upon the development of smaller optical bandgap polymers.  相似文献   

20.
    
We investigate the Amplified Spontaneous Emission (ASE) properties of a prototypical host-guest polymer polymer blend, namely poly(9,9-dioctylfluorene) (PF8) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) blend, with different concentration ratio. We show that the initial F8BT content increase causes an increase of the F8BT ASE threshold, even leading to ASE suppression for F8BT contents between 25% and 75%. ASE is then recovered upon further increase of the F8BT relative content. We demonstrate that the ASE properties of the PF8:F8BT are dominated by morphology effects, like submicrometric phase segregation, determining the net gain of the active waveguides.  相似文献   

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