聚(2-甲氧基-5-丁氧基)对苯乙炔的合成、表征及光性能研究

１９９０年,Ｂｕｒｏｕｇｈｅｓ等［１］发现聚对苯乙炔（ＰＰＶ）类衍生物不仅是导电高分子材料,而且也是性能优良的发光材料．随后,许多科学家立即将注意力集中于这类共轭聚合物的合成及光性能的研究上,并取得了可喜的研究成果［２］．目前,对ＰＰＶ衍生物的合成,...     

Mg(NH2)2-2LiH储氢材料的研究进展

Mg(NH₂)₂-2LiH 材料是近年来发展起来的几种最具应用潜力的高容量储氢材料之一. 由于具有较合适的吸放氢热力学性能、相对较低的吸放氢操作温度、较高的可逆储氢容量和较优的吸放氢循环稳定性,Mg(NH₂)₂-2LiH 材料现已成为储氢材料研究领域的一个热点. 本文综述了Mg(NH₂)₂-2LiH 材料近年来的研究进展, 重点关注了材料的组分、晶体结构、颗(晶)粒尺寸和催化动力学改性等对材料储氢性能的影响及储氢机理,总结了Mg(NH₂)₂-2LiH 储氢材料存在的技术问题并指出了今后的研究方向.     

1-(5′-溴-2′-吡啶基)-5-4′-硝基苯基)-3-(2′-呋喃基)甲(月朁)的合成及其与锌显色反应的研究

甲■类试剂是有色金属离子的优良显色剂。它们的各种取代衍生物,有许多作为分析试剂已被研究。近年来,为了改善该类试剂的分析性能,在甲(?)骨架上接上吡啶、噻唑、眯唑及呋喃等杂环基团,合成了一系列不对称型的杂环甲(?)。 本文报导5-Br-PNPFF试剂的合成和提纯方法。研究了它与锌显色反应的条件,用     

聚阴离子掺杂LiMnO_(2-y)X_y(X=BF_4~-,SiO_3~(2-),MoO_4~(2-),PO_4~(3-),BO_3~(3-))材料的合成及其电化学性能

采用水热法合成了聚阴离子掺杂LiMnO2-yXy(X=BF4-,SiO32-,MoO42-,PO43-,BO33-,y=0.01、0.03、0.05)锂离子电池正极材料。通过X射线粉末衍射(XRD)、X光电子能谱(XPS)、扫描电镜(SEM)和恒电流充放实验,研究了不同掺杂离子和掺杂量对产物结构和电化学性能的影响。结果表明,少量聚阴离子的掺杂未改变正交LiMnO2的晶体类型,但增大了材料晶胞体积,改善了材料的电化学循环性能。电化学交流阻抗(EIS)测试结果表明,聚阴离子掺杂增大了材料电荷转移阻抗,但明显提高了材料中Li+的扩散能力。     

硼化合物的研究——Ⅹ。B_(10)H_(10)~(2-)、B_(10)H_(12)~(2-)及B_3H_8~-双二茂铁季铵盐及环状二茂铁季铵盐的合成

众所周知,二茂铁类和硼氢类化合物都具有特殊的化学结构,并且有可能作为高能材料得到应用。作者通过B_(10)H_(10)~(2-)、B_(12)H_(12)~(2-)及B_3H_8~-与(N,N-二甲基胺甲基)二茂铁和1,1’-双(N,N-二甲基胺甲基)二茂铁卤化铵反应,曾合成了一系列新的化合物并研究了它们的反应性能和晶体结构。     

锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2的制备及研究

采用水热法合成了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2作为锂离子电池的正极材料,采用X-射线衍射仪(XRD)、X-射线能谱仪(EDX)、扫描电子显微镜(SEM)对其进行了表征,通过循环伏安(CV)测试、阻抗测试(EIS)和充放电测试探究了其作为正极材料的电化学性能。结果表明:该材料表现出了良好的循环性能和倍率性能,在0.2C(1C=170 mA/g)的电流密度下,其容量为160 mAh/g以上,在0.5C下,首次放电容量为143 mAh/g以上,200个循环后容量仍然有121.5 mAh/g,容量保持率在84%以上。     

C60吡咯烷键联2-(5-溴)噻吩的设计合成研究

富勒烯C60键联光活性、电活性有机功能基团获得性能优异的富勒烯C60衍生物是目前研究十分活跃的领域[1].多聚噻吩是良好的有机导体,具有高导电性能、电致发光性能等,利用其与富勒烯键联获得具有电学、磁学及生物学特性的分子,有望成为一种新型的分子器件材料.     

铽配合物[Tb(m-MBA)3phen]2·2H2O的有机电致发光

将稀土铽配合物[Tb(m MBA)3phen]2·2H2O作为发光材料应用于有机电致发光。把铽配合物掺杂在PVK中经甩膜制得发光层,并分别用AlQ和PBD作为电子传输层制作了两类有机电致发光器件。器件1:ITO PVK:[Tb(m MBA)3phen]2·2H2O PBD LiF Al;器件2:ITO PVK:[Tb(m MBA)3phen]2·2H2O AlQ LiF Al,研究了两种器件的电致发光性能,并通过选择AlQ的厚度得到了发光性能较好的用AlQ作为电子传输材料的器件,其最大亮度在20V时达到140cd·m-2。     

xLi[Li1/3Mn2/3]O2-(1-x)LiNi5/12Mn5/12Co2/12O2(0≤x≤0.8)的结构与电化学性能

采用喷雾干燥法制备了xLi[Li_1/3Mn_2/3]O₂-(1-x)LiNi_5/12Mn_5/12Co_2/12O₂(0≤x≤0.8)系列富锂层状固溶体正极材料, 并通过X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、电化学阻抗测试(EIS)以及充放电测试等多种手段研究了样品组分中Li₂MnO₃ 含量变化对材料结构及电化学性能的影响.研究发现, 材料的微观结构随着Li₂MnO₃含量的增加而逐渐发生转变.当x≤0.2时, 样品的微观结构与其母体材料LiNi_5/12Mn_5/12Co_2/12O₂相似; 而当x≥0.4时, 样品的微观结构与Li₂MnO₃有很高的相似性.当x=0.3时, 材料表现出两相共存的特征.HRTEM结果显示, 随着Li₂MnO₃含量的增加, 样品中过渡金属原子的排列逐渐由长程有序转变为长程无序而短程有序, 并且在高Li₂MnO₃含量的样品中观察到了金属阳离子混排的现象.充放电测试结果表明, 当x≤0.6时, 材料的放电比容量随着x的增加而增加; 当x>0.6时, 其放电比容量则随着x的增加而下降; 当x=0.6时, 放电比容量最高, 室温及高温(50℃)下分别为260 和304 mA·h/g.EIS研究结果表明, 这种微观结构上由有序向无序的转变会导致材料电荷转移阻抗的增加, 进而影响材料的电化学性能.     

无机-有机杂化钼磷酸盐化合物(NH_3CH_2CH_2NH_3)_2Mo_5O_(15)(HPO_4)_2的合成与表征

0引言钼磷酸盐由于具有丰富的晶体结构特点和化学特性使得这种材料在催化、离子交换剂和材料科学等领域有着更加广阔的应用前景犤1～3犦。制备化学家已采用高温和水热的方法合成了一维聚体、二维层状和三维具有敞开结构的钼磷酸盐化合物犤3～8犦。尽管钼磷酸盐化合物结构复杂以及合成条件的不可裁剪性,但我们试图通过调节化学操作来调控产物的结构和性能。最近,当利用水热技术制备这类材料时,通过调节开始材料及合成条件得到了一种新的单晶化合物(NH3CH2CH2NH3)2Mo5O15(HPO4)2,新的无水化合物的结构是由聚阴离子犤Mo5O15(HPO4)2犦4-…     

Electronic Structure Effect of Polythiophene Derivatives and Nano N-Zn-Ag/TiO2 on Performance of Organic Thin Film Solar Cell

Nanocrystal N-Zn-Ag/TiO₂ powders were prepared with N-Zn/TiO₂ by photo deposition method. A series of pure polymers P3HT[poly(3-hexylthiophene)], P3OT[poly(3-octylthiophene)], P3DT[poly(3-decylthiophene)] and P3DDT[poly(3-dodecylthiophene)], was synthesized, which were used to synthesize p-n type semiconductor materials P3HT/N-Zn-Ag-TiO₂, P3OT/N-Zn-Ag-TiO₂, P3DT/N-Zn-Ag-TiO₂ and P3DDT/N-Zn-Ag-TiO₂ by in situ che-mical method. X-Ray diffraction(XRD) and infrared(IR) spectroscopy showed the structure of the polymers and complexes. Ultraviolet-visible(UV-Vis) spectra and cyclic voltammograms(CV) showed the optical and electronic performance of the polymers and complexes. Two new single and double organic thin film heterojunction solar cells were prepared with the above mentioned synthesized powders as raw materials. Current-voltage(I-V) measurements indicate that the conversion efficiency of the single organic thin film heterojunction solar cell is higher than that of the double organic thin film heterojunction solar cells. Single organic thin film heterojunction solar cells based on P3DT/N-Zn-Ag-TiO₂ can get a photoelectric conversion efficiency of 0.0408%. The performance of electronic transform between electron donor and acceptor on organic thin film solar cells was researched.     

Engineering the interface energetics of solar cells by grafting molecular properties onto semiconductors

The electronic properties of semiconductor surfaces can be controlled by binding tailor-made ligands to them. Here we demonstrate that deposition of a conducting phase on the treated surface enables control of the performance of the resulting device. We describe the characteristics of the free surface of single crystals and of polycrystalline thin films of semiconductors that serve as absorbers in thin film polycrystalline, heterojunction solar cells, and report first data for actual cell structures obtained by chemical bath deposition of CdS as the window semiconductor. The trend of the characteristics observed by systematically varying the ligands suggests changes in work function rather than in band bending at the free surface, and implies that changes in band line-up, which appear to cause changes in band bending, rather than direct, ligand-induced band bending changes, dominate.     

AC conductivity and dielectric properties of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl)acetonitrile thin films

The dark AC conductivity and dielectric properties of thermally evaporated 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl)acetonitrile (DOPNA) thin films in sandwich structure employing symmetrical gold ohmic contacts have been investigated as function of temperature (303–443 K) and frequency (100 Hz–5 MHz). The AC conductivity, σ_AC(ω), is found to obey Jonscher’s universal power law, σ_AC(ω)=Aω^s (ω is the angular frequency). The AC conductivity of DOPNA thin films has been analyzed with reference to various theoretical models. The correlated barrier hopping is found to be the dominant conduction mechanism for charge carrier transport; the maximum barrier height, hopping length and the density of localized states are estimated. The temperature dependence of the AC conductivity shows Arrhenius type with two thermal activation energies. The activation energies are determined as a function of frequency. The behavior of the real and imaginary parts of the dielectric constant as a function of both temperature and frequency is discussed.     

Structures, electronic states, and electroluminescent properties of a zinc(II) 2-(2-hydroxyphenyl)benzothiazolate complex

Bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)(2)) is one of the best white electroluminescent materials used in organic light-emitting diodes (LEDs). Despite a large number of studies devoted to this complex, very little is known about its basic molecular and electronic structures and electron transport properties in LEDs. Therefore, we investigate the structures and electroluminescent properties. The unsolvated single crystal of Zn(BTZ)(2) was grown and its crystalline structure was determined from X-ray diffraction data. The crystal is triclinic, space group P-1, a = 9.4890(19) A, b = 9.5687(19) A, c = 11.685(2) A, alpha = 84.38(3) degrees, beta = 78.94(3) degrees, gamma = 83.32(3) degrees. The structure of the chelate is dimeric [Zn(BTZ)(2)](2) with two isotropic Zn(2+) ion centers having five-coordinate geometry. The present study provides direct evidence for the sole existence of dimeric structure in the powder and the thin film. The dimer is energetically more stable than the monomer. Analysis of the electronic structure of [Zn(BTZ)(2)](2) calculated by density functional theory reveals a localization of orbital and the distribution of four orbital "tetrads". The structural stabilities of both anion and cation and the distribution of the hole in the cation and that of the excess electron in the anion are discussed in terms of theoretical calculations. Strong intermolecular interaction may be expected to enable good electron transport properties as compared with tris(8-hydroxyquinolinato)aluminum.     

EFFECT OF WATER ON THE CONDUCTIVITY OF PPQ (ClO_4~-) COMPLEX

The preparation of conducting PPQ film was first reported in the previous paper. It is very interesting that this film is highly sensitive to moisture in air. The hydration and dehydration of the film are accompanied by change not only in color but also in conductivity and UV-visible spectrum. The conducting PPQ is reduced to PPQ and loses its conductivity after being soaked in water.     

MONOLAYER STUDIES OF 5-(4-CARB- OXYPHENYL)-10,15,20-TRITOLYL-PORPHYRIN-II. PHOTOVOLTAIC STUDY OF MULTILAYER SANDWICH CELLS*

The photovoltaic behavior of multilayer sandwich cells fabricated from the title compound has been examined. These multilayers are amorphous and contain a wide range of aggregated species. The action spectrum of the photocurrent agrees qualitatively with the absorption spectrum. This indicates that the photocurrent arises from all species in the film. The shape of the dark current-voltage characteristics varied with the porphyrin thickness. For thin films, (1 and 3 monolayers) the current can be described by a tunnelling mechanism. For thick cells (29 monolayers) the current-voltage characteristic can be fitted using either of two models: a modified Shockley equation (suggesting that the dye acts as a p-type semiconductor) or a combination of Schottky and Frenkel–Poole emission (suggesting that the porphyrin acts as an insulator). The former interpretation is preferred because it is consistent with the observed rectification characteristics; nevertheless, the latter is in agreement with the magnitude of the conductivity of the films. The power-conversion efficiencies of these cells were quite low (∼4 × 10^-4% for incident white light of intensity 2.72 W m^-2) owing to the very large internal resistance of the cells. The high resistance can be explained by observing that the molecules are in a very unfavorable orientation; maximum conductivity would be expected for the porphyrin ring systems perpendicular to the direction of current flow to give maximum overlap of the systems.     

基于CH3NH3PbI3单晶的Ta2O5顶栅双极性场效应晶体管

Organic-inorganic hybrid perovskite methylammonium lead iodide (CH₃NH₃PbI₃) generally tends to show n-type semiconductor properties. In this work, a field-effect transistor (FET) device based on a CH₃NH₃PbI₃ single crystal with tantalum pentoxide (Ta₂O₅) as the top gate dielectric was fabricated. The p-type field-effect transport properties of the device were observed in the dark. The hole mobility of the device extracted from transfer characteristics in the dark was 8.7×10^-5 cm²·V^-1·s^-1, which is one order of magnitude higher than that of polycrystalline FETs with SiO₂ as the bottom gate dielectric. In addition, the effect of light illumination on the CH₃NH₃PbI₃ single-crystal FET was studied. Light illumination strongly influenced the field effect of the device because of the intense photoelectric response of the CH₃NH₃PbI₃ single crystal. Different from a CH₃NH₃PbI₃ polycrystalline FET with a bottom gate dielectric, even with the top gate dielectric shielding, light illumination of 5.00 mW·cm^-2 caused the hole current to increase by one order of magnitude compared with that in the dark (V_GS (gate-source voltage)=V_DS (drain-source voltage)=20 V) and the photoresponsivity reached 2.5 A·W^-1. The introduction of Ta₂O₅ as the top gate dielectric selectively enhanced hole transport in the single-crystal FET, indicating that in the absence of external factors, by appropriate device design, CH₃NH₃PbI₃ also has potential for use in ambipolar transistors.     

染料敏化TiO2/WO3薄膜电池的光电变色

The light-to-electricity conversion process of the TiO2 nanostructured electrode sensitized by a dye was investigated using the photoelectrochemical method in this paper. At the same time, the WO3 thin film was electrodeposited on conducting glass. The results showed that the dye-sensitized nanoporous TiO2 film has the properties of energy conversion, along with good electrochromic properties of electrodeposited MoO3 thin film. A self-powered smart window was achieved by combining a dye-sensitized nanoporous TiO2 film as the photovoltaic layer and an electrodeposited WO3 film as the electrochromic layer. This window changed from being almost transparent to blue spontaneously under illumination, and thus could modulate light transmittance.     

Synthesis and characterization of ordered and disordered polycrystalline La(2)NiMnO(6) thin films by sol-gel

Polycrystalline La(2)NiMnO(6) thin films are prepared on Pt/Ti/SiO(2)/Si substrates by the sol-gel method. Through controlling the processing parameters, the cation ordering can be tuned. The disordered and ordered thin films exhibit distinct differences for crystal structures as well as properties. The crystal structure at room temperature characterized by X-ray diffraction and Raman spectra is suggested to be monoclinic (P2(1)/n) and orthorhombic (Pbnm) for the ordered and disordered thin films, respectively. The ferromagnetic-paramagnetic transition is 263 K and 60 K for the ordered and disordered samples respectively, whereas the saturation magnetic moment at 5 K is 4.9 μ(B) fu(-1) (fu = formula unit) and 0.9 μ(B) fu(-1). The dielectric constant as well as magnetodielectric effect is higher for the ordered La(2)NiMnO(6) thin films. The magnetodielectric effect for the ordered thin film is dominantly contributed to the intrinsic coupling of electric dipole ordering and fluctuations and magnetic ordering and fluctuations, while it is mainly contributed to Maxwell-Wagner (M-W) effects for the disordered thin film. The successful achievements of ordered and disordered polycrystalline La(2)NiMnO(6) thin films will provide an effective route to fabricate double-perovskite polycrystalline thin films by the sol-gel method.     

Design of crystal packings of styryl heterocycles and regularities of [2+2] photocycloaddition in their single crystals 8. Topochemical [2+2] autophotocycloaddition and back reaction in styryl dye of the benzothiazole series

New styryl dye of the 2-benzothiazole series was synthesized. The new dye contains two methoxy groups in the benzene ring and tosylate counterion. The [2+2] photocycloaddition (PCA) of the dye was studied in the polycrystalline film and in single crystal. Two modifications of the dye cocrystallizate with hydroquinone differed in the ratio of components were obtained, and their ability to enter PCA was studied. According to the X-ray diffraction data, molecular cations of the dye form stack packings either of syn-“head-to-tail” type or relatively isolated stacking dimers. In all cases, the ethylene bonds of the adjacent cations are brought together and antiparallel, favoring PCA to form the centrosymmetric rctt-isomer of 1,2,3,4-tetrasubstituted cyclobutane. In two cases, the PCA reaction proceeded as the “single crystal-to-single crystal” transformation. Hydrogen bonds in crystals including hydroquinone molecules strengthen the crystal packing retarding the PCA. The back photoreaction (retro-PCA) was detected: it occurs without single crystal decomposition and results in the accumulation of the initial styryl dye in crystal consisting of the cyclobutane derivative. This is the first example of such a transformation in single crystals.