We report a facile way to produce printable highly conductive cathode interfacial layer (CIL) for efficient polymer solar cells (PSCs) by sensitizing ZnO nanocrystals (NCs) with a blue fluorescent conjugated polymer, poly(9, 9-bis-(6'-diethoxylphosphorylhexyl) fluorene) (PFEP). Herein, PFEP plays dual distinctive roles in the composite. Firstly, PFEP chains can effectively block the aggregation of ZnO NCs, leading to uniform and smooth film during solution processing via assembly on ZnO NC surfaces through their pending phosphonate groups. Secondly, PFEP can greatly improve the conductivity of ZnO NCs by charge transfer doping, that is the charge transfer from the sensitizer driven by electron-chemical potential equilibrium, which could be even more pronounced under light illumination because of light excitation of PFEP sensitizer. The increased conductivity in ZnO-PFEP layer renders more efficient electron transport and extraction compared to pristine ZnO layer. This ZnO-PFEP CIL was successfully applied to PSCs based on three polymer donor systems with different band-gaps, and efficiency enhancements from 44 to 70% were observed compared to those PSCs with pristine ZnO CIL. The highest efficiency of 7.56% was achieved in P(IID-DTC):PC70BM-based PSCs by using ZnO-PFEP film as CIL. Moreover, the enhanced conductivity due to the charge-transfer doping effect allows thick ZnO-PFEP film to be used as CIL in high-performance PSCs. Both the high conductivity and good film-forming properties of ZnO-PFEP CIL are favorable for large-scale printable PSCs, which is also verified by high-efficiency PSCs with ZnO-PFEP CIL fabricated using doctor-blading, a large-scale processing technique. The work provides an efficient printable cathode interfacial material for efficient PSCs.
We demonstrate a facile and general strategy based on ligand protection for the synthesis of unstable colloidal nanocrystals by using the synthesis of pure p-type NiO nanocrystals as an example. We find that the introduction of lithium stearate, which is stable in the reaction system and capable of binding to the surface of NiO oxide nanocrystals, can effectively suppress the reactivity of NiO nanocrystals and thus prevent their in situ reduction into Ni. The resulting p-type NiO nanocrystals, a highly demanded hole-transporting and electron-blocking material, are applied to the fabrication of organic solar cells and polymer light-emitting diodes, demonstrating their great potential as an interfacial layer for low-cost and large-area, solution-processed optoelectronic devices.
A solution-processed self-powered polymer electrochromic/photovoltaic (EC/PV) device is realized by vertically integrating two transparent PV cells with an ECD. The EC/PV cell is a net energy positive dual functional device, which can be reversibly switched between transparent and colored states by PV cells for regulating incoming sunlight through windows. The two PV cells can individually, or in pairs, generate electricity.
It has been hypothesized that dysregulation of brain-expressed genes is the major predisposing underlying mechanism for autism. This dysregulation may be mediated by differential methylation of CpG sites within gene promoters, which could be candidate biomarkers and used for early clinical screening of autism. A total of 131 pairs of age- and sex-matched autistic and control subjects were recruited in this study. Peripheral blood cells were analyzed. The first five pairs were randomly applied to array-based genome-wide methylation studies. A neuron-specific gene, ENO2, was found to be hypermethylated in the autistic samples. This difference was validated by bisulfite sequencing PCR (BSP). The differential expression of ENO2 gene was further analyzed with RT-qPCR and ELISA. The hypermethylation of ENO2 within the promoter region was confirmed by BSP to be present in 14.5 % (19/131) of the total of the autistic samples. The mean ENO2 RNA level in these 19 autistic samples was reduced by about 70 % relative to that in controls. The average level of ENO2 protein expression in the 19 autistic samples (15.18?±?3.51 ?g/l) was about half of that in the controls (33.86?±?8.16 ?g/l).
Human serum albumin (HSA), a naturally abundant protein in blood plasma and tissue fluids, has an extraordinary ligand-binding capacity and is advocated as a drug carrier to facilitate drug delivery. To render it tumor targeting specificity, we generated a recombinant HSA fused with the amino-terminal fragment (ATF) of urokinase, allowing the fusion protein to bind to urokinase receptor (uPAR), which is shown to have a high expression level in many tumors, but not in normal tissues. To test the efficacy of this bifunctional protein (ATF-HSA), a hydrophobic photosensitizer (mono-substituted ?-carboxy phthalocyanine zinc, CPZ) was chosen as a cytotoxic agent. A dilution-incubation-purification (DIP) strategy was developed to load the ATF-HSA with this CPZ, forming a 1:1 molecular complex (ATF-HSA:CPZ). We demonstrated that CPZ was indeed embedded inside ATF-HSA at the fatty acid binding site 1 (FA1) of HSA, giving a hydrodynamic radius of 7.5 nm, close to HSA's (6.5 nm). ATF-HSA:CPZ showed high stability and remarkable optical and photophysical properties in aqueous solution. In addition, the molecular complex ATF-HSA:CPZ can bind to recombinant uPAR in vitro and uPAR on tumor cell surfaces, and was efficient in photodynamic killing of tumor cells. The tumor-killing potency of this molecular complex was further demonstrated in a tumor-bearing mouse model at a dose of 0.080 ?mol / kg, or 0.050 mg CPZ / kg of mouse body weight. Using fluorescent molecular tomography (FMT), ATF-HSA:CPZ was shown to accumulate specifically in tumors, and importantly, such tumor retention was higher than that of HSA:CPZ. Together, these results indicate that ATF-HSA:CPZ is not only an efficient tumor-specific cytotoxic agent, but also an useful tumor-specific imaging probe. This bifunctional protein ATF-HSA can also be used as a drug carrier for other types of cytotoxic or imaging agents to render them specificity for uPAR-expressing tumors.
In this paper, we report enhanced performance of inverted polymer solar cells composed of poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1):[6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) blends by using poly(ethylene oxide) (PEO)-modified ZnO as an electron transport layer. It is found that PEO modification to the ZnO nanoparticle surface can effectively passivate the surface traps of ZnO, suppress the recombination loss of carriers, reduce the series resistance, and improve the electrical coupling of ZnO/active layer. Consequently, both the short-circuit current (J(SC)) and the fill factor (FF) of the inverted solar cells are considerably improved. The resulting power conversion efficiency (PCE) is improved to 5.64% as compared to 4.5% of the reference device using a ZnO electron transport layer. Moreover, this approach can also successfully improve the J(SC) and FF of anther inverted solar cell composed of poly[N-9?-hepta-decanyl-2,7-carbazole-alt-5,5-(4,7-dithienyl-2,1,3-benzothiadiazole)] (PCDTBT):PC(71)BM blends. The PCE of the device based on the PEO-modified ZnO layer is increased to 6.59% from 5.39% of the reference device based on the ZnO layer.
A new, low-band-gap alternating copolymer consisting of terthiophene and isoindigo has been designed and synthesized. Solar cells based on this polymer and PC(71)BM show a power conversion efficiency of 6.3%, which is a record for polymer solar cells based on a polymer with an optical band gap below 1.5 eV. This work demonstrates the great potential of isoindigo moieties as electron-deficient units for building donor-acceptor-type polymers for high-performance polymer solar cells.
The binding of a drug to plasma protein reduces free drug in the blood circulation that would otherwise be available for penetration into tissues to reach the therapeutic target or the kidney for elimination. Therefore, the binding event affects drug elimination from the body, efficacy, duration of action and toxicity. Co-administration of other drugs, food and pathological conditions of patients can significantly change percentage binding of the drug and result in serious consequences. Here, we present the largest and newest information on plasma protein binding for 222 drugs, of which 50% show 90-100% binding, a range that could be considered as a favorable element for future lead selection. We also provide critical and comprehensive evaluations on the methods and techniques established to determine plasma protein binding, pinpoint advantages and pitfalls of individual approaches, and offer detailed guidance for experimental designs, including ultrafiltration, equilibrium dialysis, ultracentrifugation, charcoal adsorption, high-performance affinity chromatography, high-performance frontal analysis, solid-phase microextraction and in vivo microdialysis.
A new low band gap polymer (E(g) = 1.6 eV) with alternating thiophene and isoindigo units was synthesized and characterized. A PCE of 3.0% and high open-circuit voltage of 0.89 V were realized in polymer solar cells, which demonstrated the promise of isoindigo as an electron deficient unit in the design of donor-acceptor conjugated polymers for polymer solar cells.
The nitration of 4,7-dibromo-2,1,3-benzothiadiazole was modified by using CF(3)SO(3)H and HNO(3) as the nitrating agent, and the related yield was improved greatly. On the basis of this improvement, two new small band gap polymers, P1TPQ and P3TPQ, were developed. Bulk heterojunction solar cells based on P3TPQ and [6,6]-phenyl-C(71)-butyric acid methyl ester exhibit interesting results with a power conversion efficiency of 2.1% and photoresponse up to 1.1 ?m.
We have studied the influence of three different fullerene derivatives on the charge generation and recombination dynamics of polymer/fullerene bulk heterojunction (BHJ) solar cell blends. Charge generation in APFO3/PCBM and APFO3/PCBM is very similar and somewhat slower than charge generation in APFO3/BTPF. This difference qualitatively matches the trend in free energy change of electron transfer estimated from the LUMO energies of the polymer and fullerene derivatives. The first order (geminate) charge recombination rate is significantly different for the three fullerene derivatives studied and increases in the order APFO3/PCBM < APFO3/PCBM < APFO3/BTPF. The variation in electron transfer rate cannot be explained from the LUMO energies of the fullerene derivatives and single-step electron transfer in the Marcus inverted region and simple considerations of expected trends for the reorganization energy and free energy change. Instead we suggest that geminate charge recombination occurs from a state where electrons and holes have separated to different distances in the various materials because of an initially high charge mobility, different for different materials. In a BHJ thin film this charge separation distance is not sufficient to overcome the electrostatic attraction between electrons and holes and geminate recombination occurs on the nanosecond to hundreds of nanoseconds time scale. In a BHJ solar cell, we suggest that the internal electric field in combination with polarization effects and the dynamic nature of polarons are key features to overcome electron-hole interactions to form free extractable charges.
The synthesis of novel conjugated polymers, designed for the purpose of photovoltaic energy conversion, and their properties in polymer/fullerene materials and photovoltaic devices are reviewed. Two families of main-chain polymer donors, based on fluorene or phenylene and donor-acceptor-donor comonomers in alternating copolymers, are used to absorb the high-energy parts of the solar spectrum and to give high photovoltages in combinations with fullerene acceptors in devices. These materials are used in alternative photovoltaic device geometries with enhanced light incoupling to collect larger photocurrents or to enable tandem devices and enhance photovoltage.
The effort to improve the energy conversion efficiency of polymer solar cells has led to the design of novel donor polymers. To improve open circuit photovoltages (OCVs) and the spectral coverage of the solar spectrum, researchers have looked for materials with high HOMO values, an easily modified electronic structure, and sufficient electronic transport within the polymers. One advance in design from our laboratories has been the development of a class of alternating polyfluorene copolymers (APFOs), which can be combined with fullerenes to make bulk heterojunction materials for photovoltaic conversion. This Account describes copolymers of fluorene that we designed to expand the range the optical absorption of solar cells to include wavelengths out to 1000 nm. In most cases, we combine these polymers with acceptors from the fullerene family, typically the phenyl C(61) butyric acid methyl ester (PCBM) molecule, to generate solar cell materials. The synthesis of alternating copolymers of fluorene with various donor-acceptor-donor elements provides the opportunity to shift both HOMO and LUMO, which we have followed by electrochemical spectroscopy. Moving the LUMO of the APFOs farther from the vacuum level eventually leads to a situation where the driving force for photo-induced charge transfer from polymer donor to fullerene acceptor goes to zero, resulting in inefficient charge generation. Moving the HOMO level closer to the vacuum level reduces the OCV of devices made from bulk heterojunction blends. As we move the bandgap toward lower energies and increase the overlap of optical absorption with the solar spectrum, both these events eventually occur. In devices based on these APFO/fullerene blends, the performance depends on the OCV, the photocurrent under solar illumination, and the fill factor. The fill factor is influenced by electrical transport and charge generation. Optimizing these parameters requires new solutions to the perennial conflict between optically thin devices, where electrical extraction of charge is not a limitation, and the optically thick devices, where extraction of charge is hampered by trapping and recombination. As a result, we have developed methods to trap light in optically thin devices. When the thin film flexible solar cells are folded, multiple reflection between adjacent solar cells leads to a longer path length for the photon through the devices and considerable improvement of the optical dissipation in the active material. These optical tricks also enable an alternative route to tandem devices, where two different bandgap materials are located on adjacent folds. Thus light not absorbed in one cell is reflected onto the next cell to produce an effective optical series arrangement. Using experiments and simulations of the light trapping effects, we demonstrate power conversion efficiency enhancements of up to a factor of 1.8.
An alternating copolymer, poly(2-(5-(5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo[c][1,2,5]thiadiazol-7-yl)thiophen-2-yl)-9-octyl-9H-carbazole) (HXS-1), was designed, synthesized, and used as the donor material for high efficiency polymer solar cells. The close packing of the polymer chains in the solid state was confirmed by XRD. A J(sc) of 9.6 mA/cm(2), a V(oc) of 0.81 V, an FF of 0.69, and a PCE of 5.4% were achieved with HXS-1 and [6,6]-phenyl C(71)-butyric acid methyl ester (PC(71)BM) as a bulk heterojunction active layer spin-coated from a solvent mixture of 1,2-dichlorobenzene and 1,8-diodooctane (97.5:2.5) under air mass 1.5 global (AM 1.5 G) irradiation of 100 mW/cm(2).
Conjugated polymers as electron donors in solar cells based on donor/acceptor combinations are of great interest, partly due to the possibility of converting solar light with a low materials budget. Six small bandgap polymers with optical bandgap ranging from 1.0-1.9 eV are presented in this paper. All polymers utilize an electron donor-acceptor-donor (DAD) segment in the polymer backbone, creating a partial charge-transfer, to decrease the bandgap. The design, synthesis and the optical characteristics as well as the solar cell characteristics of the polymers are discussed. The positions of the energy levels of the conjugated polymer relative to the electron acceptor are of significant importance and determine not only the driving force for exciton dissociation but also the maximum open-circuit voltage. This work also focuses on investigating the redox behavior of the described conjugated polymers and electron acceptors using square wave voltammetry. Comparing the electrochemical data gives important information of the structure-property relationships of the polymers.
In this article we report the weak but omnipresent electroluminescence (EL) from several types of organic polymer:fullerene bulk heterojunction solar cells biased in the forward direction. The light emitted from blends of some commonly used polymers and the fullerene molecule is significantly different from that of any of the pure materials comprising the blend. The lower energy of the blend EL is found to correlate with both the voltage onset of emission and the open-circuit voltage of the photovoltaic cell under solar illumination. We accordingly interpret the emission to originate from interfacial charge transfer state recombination and emphasize EL as a very valuable tool to characterize the charge transfer state present in donor/acceptor organic photovoltaic (OPV) cells.
Evaluating six main rivers and six lakes in Beihuan water system (BWS) and diagnosing the limiting factors of eco-health were conducted for the ecohealth assessment and ecological restoration division of urban water system (UWS) for Beijing. The results indicated that Jingmi River and Nanchang River were in a healthy state, the degree of membership to unhealthy were 0.358, 0.392, respectively; while Yongding River, Beihucheng River, Liangma River, Tongzi River and six lakes were in an unhealthy state, their degree of membership to unhealthy were between 0.459 and 0.927. The order of that was Liangma > Beihucheng > Tongzi > Yongding > six lakes > Jingmi > Nanchang, in which Liangma Rivers of that was over 0.8. The problems of Rivers and lakes in BWS are different. Jingmi River and Nanchang River were ecotype limiting; Yongding River, Tongzi River and six lakes were water quality and ecotype limiting. Beihucheng River and Liangma River were water quantity, water quality and ecotype limiting. BWS could be divided into 3 restoration divisions, pollution control division including Yongding River, Tongzi River and six lakes; Jingmi River and Nanchang River were ecological restoration zone, while Beihucheng River and Liangma River were in comprehensive improvement zone. Restoration potentiality of Jingmi River and Nanchang River were higher, and Liangma River was hardest to restore. The results suggest a new idea to evaluate the impact of human and environmental factors on UWS.
A method for CdSe quantum dot (QD) sensitization of ZnO nanowires (NW) with fast adsorption rate is applied. Photoinduced excited state dynamics of the quantum dots in the case of more than monolayer coverage of the nanowires is studied. Transient absorption kinetics reveals an excitation depopulation process of indirectly attached quantum dots with a lifetime of ~4 ns. Photoluminescence and incident photon-to-electron conversion efficiency show that this process consists of both radiative e-h recombination and nonradiative excitation-to-charge conversion. We argue that the latter occurs via interdot energy transfer from the indirectly attached QDs to the dots with direct contact to the nanowires. From the latter, fast electron injection into ZnO occurs. The energy transfer time constant is found to be around 5 ns.
The efficiency of conversion of light to electrical energy with the help of conjugated polymers and molecules is rapidly improving. The optical absorption properties of these materials can be designed, and implemented via molecular engineering. Full coverage of the solar spectrum is thus feasible. Narrow absorption spectra allow construction of tandem solar cells. The poor transport properties of these materials require thin devices, which limits optical absorption. Alternative device geometries for these flexible materials compensate for the optical absorption by light trapping, and allow tandem cells.
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