两步法制备CIGS薄膜的工艺研究

本文主要研究了"预制层硒化法"制备铜铟镓硒(CIGS)薄膜的工艺。采用磁控溅射的方式制备In、Cu-Ga金属预制层,然后进行硒化(450℃)以及退火处理(550℃)。SEM结果表明,在室温下溅射沉积In薄膜,并且采用Mo/Cu-Ga/In/Cu-Ga/In的叠层顺序,可以获得平整致密的CIGS薄膜。XRD和SEM测量显示,以单质硒作为硒源,在450℃的硒化之后生成分离的CIS和CGS相,惰性氛围的高温退火可以使分离的CIS和CGS相互融合,形成均一化的CIGS四元化合物。在此基础上,最终完成的CIGS电池光电转换效率为7.5%。     

Structural Characterization and Toxicity Prediction of Some Organic Compounds

A new molecular structural characterization(MSC)method called molecular vertexes correlative index(MVCI)was constructed in this paper.The index was used to describe the structures of 45 compounds and a quantitative structure-activity relationship(QSAR)model of toxicity(–lgEC50)was obtained through multiple linear regression(MLR)and stepwise multiple regression(SMR).The correlation coefficient(R)of the model was 0.912,and the standard deviation(SD)of the model was 0.525.The estimation stability and prediction ability of the model were strictly analyzed by both internal and external validations.The Leave-One-Out(LOO)Cross-Validation(CV)correlation coefficient(RCV)was 0.816 and the standard deviation(SDCV)was 0.739,respectively.For the external validation,the correlation coefficient(Rtest)was 0.905 and the standard deviation(SDtest)was 0.520,respectively.The results showed that the index was superior in molecular structural representation.The stability and predictability of the model were good.     

高性能核壳结构催化剂PdRu@Pt/CNT的制备

采用两步沉积还原法制备了一种以PdRu合金为核、以铂为壳,以碳纳米管(CNT)为载体的核壳结构低铂催化剂PdRu@Pt/CNT.该催化剂对于甲醇催化氧化的单位位质量铂的活性可达自制20%Pt/CNT催化剂的1.7倍,且其正扫和反扫峰的峰电流密度之比(/_f//_b)高达2,是Pt/CNT催化剂/_f//_b值的2倍,表明通过将活性组分铂分散在PdRu核上,有效地提高了金属铂的分散度和铂的利用率,且通过壳层铂原子与核中钌及钯的相互作用,大大提高了催化剂对甲醇氧化中间体的去除能力.X射线衍射(XRD)和透射电子显微镜(TEM)的结果揭示了催化剂的核壳结构.另外,从TEM还可以看出:活性组分均匀地分布在碳纳米管载体上,活性组分粒径约为4.0 nm.由于这种催化剂能够有效提高铂的利用效率,并且有效消除甲醇氧化中间体,在低温燃料电池领域具有良好的应用前景.     

Photoinduced Charge Transfer Processes of Zinc Porphyrin Derivatives for Dye-sensitized Solar Cells

We studied the excitation energies of zinc porphyrin(ZnP) and zinc porphyrin analogues(ZnP-R) with long-range corrected(LC) density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was found that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G(d) basis set. Excited-state geometry optimizations for all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc(F)₁₂] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis(4-hexylphenyl)amino] partially. The computed excited-state radiative lifetime(τ) for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur after vibrational relaxation of excited state.     

基于对叔丁基杯[8]芳烃的3d-5f核簇化合物（MxThy, M=Co、Ni、Zn）的合成、结构与磁性研究

本文以对叔丁基杯[8]芳烃（H₈C₈A）为配体,在溶剂热条件下制得了3个3d-5f化合物,[Co₂Th₄（HC8A）₂O₂（OH）₂（DMF）₆]（1）、[Ni₂Th₅（H₂C8A）（C₈A）O₄（OH）₂（DMF）₅（CH₃OH）₂]（2）、[Zn₂Th₆（HC8A）（C8A）O₅（CH₃O）（C₃H₆NO₂）₂（DMF）₅（CH₃OH）]（3）（其中H₈C8A=对叔丁基杯[8]芳烃,DMF=N,N-二甲基甲酰胺）。X-射线单晶测试表明,这3个化合物均为2个以尾对尾方式排列的杯[8]芳烃分子中间夹1个3d-5f核簇的三明治型结构。杯[8]芳烃均表现为双锥式构型,且每个锥式空腔下缘结合1个钍离子,双锥的连接处及2个杯芳烃分子之间由过渡金属离子或钍离子连接。不同过渡金属离子不同的配位环境导致3种不同核簇的形成。化合物1的磁性研究表明,该化合物在低温下表现出弱铁磁性相互作用。     

水热合成LuF3∶Yb3+，Er3+微晶及其上转换发射与温度传感特性

通过在不同pH值下的简易水热法合成不同Yb³⁺离子（n_Yb³⁺/n_Lu³⁺=5%~15%）和Er³⁺离子（n_Er³⁺/n_Lu³⁺=1%~5%）掺杂浓度的LuF₃∶Yb³⁺,Er³⁺微晶荧光粉。发现pH值对正交相LuF₃∶Yb³⁺,Er³⁺的合成起着关键作用。在980 nm激发下,LuF₃∶Yb³⁺,Er³⁺荧光体呈现出以523 nm（²H_11/2→⁴I_15/2）和539 nm（⁴S_3/2→⁴I_15/2）为中心的强绿光上转换（UC）发射以及以660 nm（⁴F_9/2→⁴I_15/2）为中心弱红光上转换发射。通过使用X射线衍射（XRD）和光致发光（PL）分析测定了最强发射强度的Er³⁺和Yb³⁺的最佳掺杂浓度。浓度依赖性研究表明,达到最强的绿光上转换发光时最佳掺杂浓度为10% Yb³⁺,2% Er³⁺。通过改变泵浦功率来研究LuF₃∶Yb³⁺,Er³⁺荧光粉UC发光机制。通过980 nm二极管激光器在293~573 K的范围内研究了在523和539 nm处的2个绿光UC发射带的荧光强度比（FIR）的温度依赖性,发现在490 K得到最大灵敏度约为15.3×10^-4 K^-1。这表明LuF₃∶Yb³⁺,Er³⁺荧光体可应用于具有高灵敏度的光学温度传感器。     

IN situ Confocal Microprobe Raman Spectroscopic Studies on Defective La-based Complex Oxides

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丙烯酸酯/液晶复合体系的光聚合动力学

采用光差示扫描量热分析,研究了以2, 4, 6-三甲基苯甲酰基-二苯基氧化膦(TPO)为光引发剂、丙烯酸异辛酯(EHA)和三羟甲基丙烷三甲基丙烯酸酯(TMPTA)为单体、液晶为P0616A的丙烯酸酯/液晶复合体系在-40~80℃的光聚合动力学。研究表明：丙烯酸酯/液晶复合体系光聚合的自动加速现象非常显著,聚合反应速率和表观动力学常数在聚合过程中均存在最大值。随着反应温度的提高,体系的最终转化率、最大聚合反应速率(Rpmax)均明显提高,当反应温度高于20℃后,其增长均趋于平缓。随着体系中液晶含量的增加,体系的Rpmax呈下降趋势,体系的聚合反应转化率随时间的增长速率较慢,但是最终转化率差别不大,均接近80%。随着UV光强的增高,体系的Rpmax和最终转化率均明显提高, 体系的阈值光强约为4 mw/cm2。而随着体系平均官能度的增加,体系的Rpmax和最终转化率则呈下降的趋势。     

Photocatalytic and Photoelectronic Properties of Anatase TiO2 Modified by Cu Ions Plasma and Its Theoretic Study by the First Principle Study

<正>Highly ordered anatase titania nanotube arrays (TiNT) were fabricated by anodic oxidation. SEM analysis method was used to characterize the morphology of the prepared samples. TiNT samples doped with Cu ions were prepared by home-made Metal Vapor Vacuum Arc ions sources (MEVVA, BNU, China) implanter. Photo-electric response and methyl orange decomposition ability of implanted samples under UV and visible light were tested, and the results indicated that the performance of Cu/TiNT enhanced significantly under visible light; it was noteworthy that the photocurrent density of A-Cu/TiNT was 0.102 mA/cm~2, which was 115 times that of pure TiNT, and degradation ability of TiNT also strongly enhanced under visible light. In a word, the absorption spectrum of implanted anatase titania shifted to a longer wavelength region. Theoretic study on Cu-doped anatase based on density functional theory was carried out in this paper to validate the experiment results. The calculation results are depicted as follows: Intermittent energy band appeared around the Fermi energy after doping with Cu metal, the width of which was 0.35 eV and the location of valence and conduction bands shifted to the lower energy level by 0.22 eV; more excitation and jump routes were opened for the electrons. The narrowed band gaps allowed the photons with lower energy (at longer wavelength, such as visible light) to be absorbed, which accorded well with the experimental results.     

合成宾达利的新方法

以邻氨基苯乙酮(2)为原料,经过连续的重氮化-还原-缩合反应序列制得3-甲基-1H-吲唑(3);3经(Boc)2O保护亚氨基后以NBS进行甲基溴代反应制得1-叔丁氧羰基-3-溴甲基-1H-吲唑(5);5与2-羟基异丁酸乙酯缩合得醚2-(1-叔丁氧羰基-1H-吲唑-3-基)甲氧基-2-甲基丙酸乙酯(6);6经HCl/乙酸乙酯溶液脱Boc保护制得关键中间体7;在叔丁醇钾存在下,7与溴苄缩合并水解合成了MCP-1抑制剂宾达利,总收率37.3%,其结构经1H NMR,13C NMR和MS确证。