Organic photovoltaic cells using hexadecafluorophthalocyaninatocopper (F16CuPc) as electron acceptor material

We fabricated organic photovoltaic cells by using hexadecafluorophthalocyaninatocopper (F16CuPc) as electron acceptor material and para-sexiphenyl (p-6P) as electron donor material. F16CuPc has wide absorption spectrum from 550 nm to 850 nm, which covers the maximum of solar photo flux. The measurement of their external quantum efficiency (EQE) demonstrated that the photocurrent comes from the excitons created in F16CuPc, which were separated into free electrons and holes at heterojunction interface of p-6P and F16CuPc. Moreover, F(16)FuPc with excellent air-stability improved the environmental stability of photovoltaic cells, and the unencapsulated cells exhibited the shelf lifetime of exceeding a week.

Organic light emitting diodes using magnesium doped organic acceptor as electron injection layer and silver as cathode

Organic light emitting diodes employing magnesium doped electron acceptor 3, 4, 9, 10 perylenetetracarboxylic dianhydride (Mg: PTCDA) as electron injection layer and silver as cathode were demonstrated. As compared to Mg: Ag cathode, the combination of the Mg: PTCDA layer and silver provided enhanced electron injection into tris (8-quinolinolato) aluminium. The device with 1: 2 Mg: PTCDA and Ag showed an increase of about 12% in the maximum current efficiency, mainly due to the improved hole-electron balance, and an increase of about 28% in the maximum power efficiency, as compared to the control device using Mg: Ag cathode. The properties of Mg: PTCDA composites were studied as well.

Improved performance in organic light emitting diodes with a mixed electron donor-acceptor film involved in hole injection

Organic light emitting diodes using a mixed layer of electron acceptor 3, 4, 9, 10 perylenetetracarboxylic dianhydride and electron donor copper phthalocyanine (PTCDA:CuPc) on indium tin oxide (ITO) anodes were fabricated. The device properties were found to be strongly dependent on the thickness of the PTCDA:CuPc film: both the power efficiency and the driving voltage of the device were optimized with a thickness of PTCDA:CuPc ranging from 10 to 20 nm. As compared to the conventional ITO/CuPc hole injection structure, the ITO/PTCDA:CuPc hole injection structure could remarkably enhance both the luminance and the power efficiencies of devices. A mechanism of static-induced, very efficient hole-electron pairs generation in mixed PTCDA:CuPc films was proposed to explain the experimental phenomena. The structural and optical properties of PTCDA:CuPc film were examined as well. (c) 2007 American Institute of Physics.

新型光系统II电子传递抑制剂的抑制特性及作用位点的研究

本文由两部分组成，一部分是关于一组新型除草剂(K-15，K-23)的抑制特性及作用位点的研究;另一部分是关于碳酸氢盐对细胞色素b-559高电势的保护作用的研究。 在第一部分，我们首先研究了抑制剂K-23对Psn放氧活性、DCIP光还原和可变荧光等光合特性的影响。研究发现，K-23在低浓度时刺激放氧活性，而在相对高浓度时抑制放氧活性。但是，K-23在低浓度时却有效地抑制了可变荧光。这些数据表明了新型抑制剂的抑制反应是基于氧化还原作用而不是猝灭作用。此外，通过采用胰蛋白酶消化类囊体膜的方式初步检测了新型抑制剂的作用部位，其结果表明：虽然新型抑制剂抑制受体侧电子传递，但它的抑制部位与DCMU不同。 其次，研究了新型抑制剂对光系统II色素蛋白复合体与多肽组分的影响及抑制剂的键合蛋白。应用SDS-PAGE技术，发现新型抑制剂主要作用于光系统II的反应中心蛋白。用温和的Deriphat-PAGE分析也证实了新型抑制剂作用于核心复合物，导致核心复合物二聚体消失。 进一步用SDS-PAGE分析新型抑制剂对Psn多肽组分的影响，发现新型抑制剂主要影响D．、D2、CP43和CP47。用荧光发射的方法确定了K-15键合在D2蛋白上。 最后，结合荧光动力学和HPLC方法，分别从定性和定量的角度，以核心复合物以及抑制剂存在下从BBY中分离的核心复合物为研究对象，详细研究了抑制剂对QA的取代作用。研究发现，在无去垢剂或低浓度去垢剂存在情况下，由于不能创造出适合于QA存在的疏水环境，我们没有得到QA被K-15取代的实验证据。而在抑制剂K-15存在下，用2.2% HTG从BBY分离的核心复合物的实验中，检测不到正的可变荧光Fv，而是得到了降低的FM，这个结果表明QA已被抑制剂在它的作用位点处所取代。 在第二部分，研究了pH5.0—7.0范围内碳酸氢盐对Cyt b-559氧化还原状态转变的影响。首先研究了pH5.0～7.0条件下碳酸氢盐对PSII Cyt b-559还原减氧化差异吸收光谱的影响，发现铁氰化钾还原的PSII Cyt b-559 HP的含量随介质pH值的降低而减少。然而，碳酸氢盐的加入阻止了由于介质pH降低而引起的Cyt b-559由高电势向低电势的转化。比如，当样品温育在pH5.0的介质中，铁氰化钾还原的Cyt b-559 HP含量占总量的25%-30%，当介质中加入2mmol/L碳酸氢盐后Cyt b-559 HP的含量上升，占总量的50%-56%。碳酸氢盐效应对氢醌还原的Cyt b-559HP含量的影响尤为显著。pH6.5时碳酸氢盐对Cyt b-559的还原氧化状态的影响不显著。其次，分别研究了PSII经Tris处理去除锰簇和三个外周蛋白及NH20H处理去除锰簇和17 kDa和23 kDa后，碳酸氢盐对Cytb一559 HP影响的pH依赖值，发现不论在pH5.0还是pH6.5的介质中碳酸氢盐效应都不存在。 综合以上实验结果，我们认为碳酸氢盐对酸化引起的Cyt b-559氧化还原状态的影响与它和锰的作用有关，但也不能排除钙离子与碳酸氢盐之间的协同作用。

ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

无介体双室微生物燃料电池产电性能初步研究

本文对无介体双室微生物燃料电池的产电性能进行了初步研究，并根据不同运行阶段产电性能的优劣，对其中微生物的差异性进行了比较分析。全文分为两个部分： 第一部分：以乙酸钠为阳极原料构建双室微生物燃料电池（MFC），研究不同阴极受体、外接电阻、乙酸钠浓度和pH等因素对电池产电性能的影响，研究结果表明：在500mL的阴阳极反应体系中，选用乙酸钠作为阳极底物，质量浓度为6.46 g/L， pH 7.0，接入500Ω外电阻，阴极电子受体选择高锰酸钾的情况下，微生物燃料电池产电性能最好，最大电功率密度达到294.72 mW/m2，库伦效率能达到25.87%。在确定最适外接电阻阻值的同时对MFC内阻进行测定，阻值为871.87Ω。 第二部分：微生物燃料电池运行中，比较以厌氧污泥作为接种源的第一阶段和只接入附着有大量微生物电极的第二阶段的产电性能，得出第二阶段产电性能优于第一阶段，最大电功率密度达到353.57mW/m2，比第一阶段提高58.85 mW/m2；库伦效率为39.35%，增幅达52％左右；针对微生物燃料电池运行过程中，底物CH3COONa可能存在其它的代谢途径，本实验进行了第二阶段产电性能与CH3COONa消耗率关系以及阳极液面上方气体成分和含量的研究，发现第二阶段50h前CH3COONa的大量消耗主要用于微生物的生长，在整个运行过程中，阳极液面上方含有CH4和CO2；对气体测定的同时还发现，振荡能增强电功率密度的输出；通过对电极上和污泥中微生物差异性分析得出，δ-变形菌纲、β-变形菌纲和拟杆菌门的菌种更适应微生物燃料电池的运行环境，能在电极上大量富集，提高电池的产电性能，只接入附着有大量微生物的电极能有效降低热袍菌纲的菌种数量，降低了CH3COONa的无为消耗，有效提高了电池的库伦效率。 Electricity production in the mediator-less two-chambered microbial fuel cell(MFC) was researched. Based on the result in the different operation phase in the MFC, the microbial diversity was analysed. The paper involved two parts: Part 1: A two-chambered microbial fuel cell (MFC) was constructed with high-concentration sodium acetate as fuel in the anode. The influence of different electron acceptors in the cathode, external resistance value, pH value and concentration of sodium acetate on electricity generation in MFC was investigated. The result showed that the maximum power density of 294.72 mW/m2 and the coulombic efficiency of 25.87% was achieved at sodium acetate concentration of 6.46 g/L, pH 7.0, external resistance 500Ωin the anode and when using potassium permanganate as electron acceptor in the cathode. While decided the value of resistor, we found that shaking has effect on electricity production in the MFC. Part 2: Comparing the electricity production in different operation phases when using anaerobic sludge as inoculum in the first phase and microbes in the anodic electrode as inoculum in the second phase, the result showed that electricity production in the second phase was more than that in the first phase, the maximum power density of 353.57 mW/m2 and the coulombic efficiency of 39.35% was achieved, 58.85 mW/m2 and 52％ more than that in the first phase, respectively. According to the fact that CH3COONa might be metabolized in other pathway in the running process in the MFC, we determining the relationship between electricity production and CH3COONa consumption, and the gas content in the anode, we found that CH3COONa was mainly used for microbe growth before 50h, and the anode contained CH4 and CO2. At the same time, we found that shaking could improve power density. The analysis on diversity of microbe in the anodic electrode and anaerobic sludge showed that δ-proteobacterium, β-proteobacterium and Bacteroidetes adapted themselves to the running environment of MFC. The anode could enrich them to improve the electricity production while reduced the quantity of Thermotogales, which were obligately anaerobic organotrophs with a fermentative metabolism, to increase the coulombic efficiency effectively.

Epitaxy-Assisted Creation of PCBM Nanocrystals and Its Application in Constructing Optimized Morphology for Bulk-Heterojunction Polymer Solar Cells

PCBM (a C-60 derivative) is so far the most successful electron acceptor for bulk-heterojunction polymer photovoltaic (PV) cells. Here we present a novel method epitaxy-assisted creation of PCBM nanocrystals and their homogeneous distribution in the matrix using freshly cleaved mica sheet as the substrate. The highly matched epitaxy relationship between the unit cell of PCBM crystal and crystallographic (001) surface of mica induces abundant PCBM nuclei, which subsequently develop into nanoscale crystals with homogeneous dispersion in the composite film.

Synthesis and Application of Thiadiazoloquinoxaline-Containing Chromophores as Dopants for Efficient Near-Infrared Organic Light-Emitting Diodes

series of a donor-acceptor-donor type of near-infrared (NIR) fluorescent chromophores based on [1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ) as an electron acceptor and triphenylamine as an electron donor are synthesized and characterized. By introducing pendent phenyl groups or changing the pi-conjugation length in the TQ core, we tuned tile energy levels of these chromophores, resulting in the NIR emission in a range from 784 to 868 nm. High thermal stability and glass transition temperatures allow these chromophores to be used as dopant emitters, which can be processed by vapor deposition for the fabrication of organic light-emitting diodes (OLEDs) having the multilayered structure of ITO/MoO3/NPB/Alq(3):dopant emitter/BCP/Alq(3)/LiF/Al. The electroluminescence spectra of the devices based on these new chromophores cover a range from 748 to 870 nm. With 2 wt % of dopant 1, the LED device shows an exclusive NIR emission at 752 nm with the external quantum efficiency (EQE) as high as 1.12% over a wide range of current density (e.g., around 200 mA cm(-2)).

Rational Design, Synthesis, and Optical Properties of Film-Forming, Near-Infrared Absorbing, and Fluorescent Chiromophores with Multidonors and Large Heterocyclic Acceptors

A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study., and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol(-1)) and non-coplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C-61 butyric acid methyl ester leads to a red shift in the absorption on]), for la and 2a. An interesting NIR electrochromism was found for 2a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore.

油气、微生物与砂岩型铀矿形成关系研究——以东胜铀矿床和钱家店铀矿床为例

Sandstone-type uranium deposits are frequently found close to oil fields or uraniferous sandstones contain bitumen or petroleum. However, few evidence has been presented to indicate the association of uranium mineralization with petroleum oxidation. Thus, Dongsheng uranium deposit in Ordos Basin and Qianjiadian deposit in Kailu Basin are taken for examples to solve the puzzle. Integration data from sedimentary petrology, mineralogy, race elements geochemistry, isotope geochemistry and organic geochemistry, the uranium and petroleum sources, and diagenetic paragenesis of the host sandstone are analyzed, and then the genetic relationship between microbes, petroleum and uranium deposits are discussed. The observation under microscope shows that the host sandstone samples from Middle Jurassic Zhiluo Formation in the Dongsheng deposit contained different kinds of metamorphic rock fragments, which should have been derived form outcrops north to this basin. The LREE/HREE ratios of gneiss and amphibolite sampled from outcrops were close to the highest and the lowest LREE/HREE ratios of the sandstones with well-compared chondrite-normalized REE patterns, respectively. So these results consistently indicated that parent rocks of sandstones were mainly contributed from these two kinds of metamorphic rocks. There was very high Th/U ratio for granite gneiss, which was a mainly potential U resource. Hydrocarbon inclusions and adsorbed hydrocarbons are observed under fluorescence microscope in the host sandstone of Dongsheng uranium deposit, suggesting that the sandstones may have been utilized as oil migration pathways. Based on biomarker parameters, it is indicated that the inclusion oils and adsorbed hydrocarbons were marginally mature to mature, and were derived from humic-sapropel type organic matter under poor reducing freshwater to semi-saline environment. The features are similar to those of organic matter extracted from Triassic sandstone and source rock, but are different from that of cretaceous sandstone. Thus, it can be concluded that the inclusion oils and adsorbed hydrocarbons were mainly derived from Triassic lacustrine facies source rock. Observation results under Scanning Electron Microscopy and Electron Microprobe with Energy Spectrum Analysis show that, in Dongsheng area, the main uranium ore mineral is coffinite. The coffinite is intimately intergrown or coexists with pyrite and calcite, thus, the solution during mineralization stage is inferred to be alkaline. The alkaline environment is not favored for uranium to be pre-concentrated by absorption, and then be reduced abiogenetically. δ34S of pyrite and δ13C of calcite indicate that pyrite was formed by bacterial sulfate reduction (BSR) and part of the carbon of calcite has been dirived from oxidation of petroleum, respectively. Additionally, petroleum is found biodegraded. All the lines of evidence consistently indicate that petroleum was involved in uranium mineralization. Coffinite with microbe-like structures is found in the high U sandstone samples and is composed of nanoparticles, indicating the coffinite is biogenic. The conclusion are also supportted by laboratory experiment studies, which have shown that SRB are capable of utilizing U(VI) as the preferred electron acceptor for respiration and reduce U(VI) to U(IV) directly, coupled the oxidaton of organic matter and sulfate reduction. Based on the research results mentioned above, in the Dongsheng area, coffinite is likely to have formed by mixing of brine containing petroleum derived from Triassic with uranium-bearing meteoric water from outcrops north to Ordos Basin. SRB utilize hydrocarbon as carbon source, and directly reduce U(VI) resulting in precipitation of coffinite. The product of metabolism, H2S and CO2, was precipitated as pyrite and calcite during mineralization stage. Petroleum in fluid inclusions and adsorbed type in host sandstone from Lower Cretaceous Yaojia Formation in Qianjiadian uranium deposit, Kailu Basin, are derived from Jurassic Jiufotang Formation in this basin and the uranium mineral consists mainly of pitchblende. The δ34S and δ13C values of pyrite and calcite during mineralization stage indicate SRB have likely degraded petroleum, which is similar to that of Dongsheng deposit. The alkaline environment as indicated by the diagenetic mineral assemblage calcite, Fe dolomite, pyrite and pitchblende deposit suggests that U ore in the Qiangjiajiadian has a similar origin, i.e., direct reduction by SRB. However, less part of pitchblende is intergrown with kaolinite, suggesting the solution during mineralization stage is acidic. The environment is favorable for U(VI) to be adsorded on quartz or other mineral, and then reduced by H2S produced by SRB. Thus, it can be concluded that U(VI) reduction with petroleum oxidation by SRB and other microbes is an important ore-forming mechanism in petroleum-related sandstone-type uranium deposits. The finding is significant in that it provides a theoretical basis for exploration of both uranium and petroleumr.

A new strategy of enhancing two-photon absorption in benzothiazole-containing fluorene molecules: Introduction of auxiliary donor-acceptor effects

A series of benzothiazole-containing fluorene molecules have been designed and their one- and two-photon absorption properties have been investigated theoretically by using the ZINDO method. The effects of electron-excessive/deficient heterocyclic bridges as auxiliary donors (auxD)/acceptors (auxA) on TPA cross-sections were studied. The results show that the molecules with D-pi-auxA-A, D-aux D-pi-A, or D-auxD-pi-auxA-A structure types have large TPA cross-section, which can be a valuable strategy in the design of two-photon absorption materials. Also, a linear relationship between the first hyperpolarizability and the TPA cross-section is observed. (c) 2006 Elsevier B.V. All rights reserved.

Electron irradiation induced defects in high temperature annealed InP single crystal

Electron irradiation induced defects in InP material which has been formed by high temperature annealing undoped InP in different atmosphere have been studied in this paper. In addition to Fe acceptor, there is no obvious defect peak in the sample before irradiation, whereas five defect peaks with activation energies of 0.23 eV, 0.26 eV, 0.31 eV, 0.37 eV and 0.46 eV have been detected after irradiation. InP annealed in P ambient has more thermally induced defects, and the defects induced by electron irradiation have characteristics of complex defect. After irradiation, carrier concentration and mobility of the samples have suffered obvious changes. Under the same condition, electron irradiation induced defects have fast recovery behavior in the FeP2 ambient annealed InP. The nature of defects, as well as their recovery mechanism and influence on material property have been discussed from the results.