有机芳香烃掺杂控制C_(60)微/纳米晶形貌和发光

C60高度的分子对称性使其能带间的电子跃迁被禁止,导致其发光很弱。为了提高C60纳米晶的发光强度,采用挥发C60的芳香烃饱和溶液的方法,一步合成了芳香烃溶剂化的C60纳米晶。实验结果表明,有机溶剂的掺杂在不同程度上增强了C60纳米晶的发光,其原因可能是溶剂的掺杂破坏了C60的高度的分子对称性。     

A DOUBLE-TEMPERATURE-GRADIENT TECHNIQUE FOR THE GROWTH OF PURE C60 SINGLE CRYSTALS FROM THE VAPOR PHASE

Pure C₆₀ single crystals were grown by a sublimation-condensation method in an evacuated dosed quartz tube situated in a double-temperature-gradient furnace. Large C₆₀ single crystals, up to a size of 0.6 mm×1.0 mm×2.0 mm with quite smooth and shiny faces, were obtained. X-ray diffraction, electron diffraction and X-ray morphology were carried out and showed that the quality of large C₆₀ single crystals grown by the double-temperature-gradient technique is excellent. In this paper the experimental results of the growth of large C₆₀ single crystals are reported and the morphological and structural characterizations are discussed in detail.     

A new carbon solid made of the world's smallest caged fullerene C20

Caged fullerene C₂₀ solids were successfully synthesized by means of ion beam irradiation method. The characterization of structures and features of C₂₀ crystal have been performed using various complementary analysis techniques, such as high-resolution transmission electron microscope, electron diffraction, laser desorption post-ionization, and Raman spectroscopy. These results indicate that in condensed phases C₂₀ molecules can act as dodecahedron carbon cages; in particular the capability of acting as a building blocks of hexagonal crystal.     

Characterization of atomic-layer MoS_2 synthesized using a hot filament chemical vapor deposition method

Atomic-layer MoS_2 ultrathin films are synthesized using a hot filament chemical vapor deposition method. A combination of atomic force microscopy(AFM), x-ray diffraction(XRD), high-resolution transition electron microscopy(HRTEM), photoluminescence(PL), and x-ray photoelectron spectroscopy(XPS) characterization methods is applied to investigate the crystal structures, valence states, and compositions of the ultrathin film areas. The nucleation particles show irregular morphology, while for a larger size somewhere, the films are granular and the grains have a triangle shape. The films grow in a preferred orientation(002). The HRTEM images present the graphene-like structure of stacked layers with low density of stacking fault, and the interlayer distance of plane is measured to be about 0.63 nm. It shows a clear quasihoneycomb-like structure and 6-fold coordination symmetry. Room-temperature PL spectra for the atomic layer MoS_2 under the condition of right and left circular light show that for both cases, the A1 and B1 direct excitonic transitions can be observed. In the meantime, valley polarization resolved PL spectra are obtained. XPS measurements provide high-purity samples aside from some contaminations from the air, and confirm the presence of pure MoS_2. The stoichiometric mole ratio of S/Mo is about 2.0–2.1, suggesting that sulfur is abundant rather than deficient in the atomic layer MoS_2 under our experimental conditions.     

梯度掺杂体异质结对有机太阳能电池光电转换效率的影响

基于传统的体异质结有机太阳能电池结构, 对结构中的混合层改用梯度掺杂的方法, 在AM1.5, 100 mW/cm²光照下, 使得器件的短路电流由原来的7.72 mA/cm²提高到了9.18 mA/cm², 相应的光电转换效率提高了25%. 器件性能的提升归因于梯度掺杂体系的引入使得体异质结混合层中同一材料分子之间形成了较好的连续网络结构, 降低了器件的串联电阻, 提高了电极对载流子的收集效率, 从而提高了器件的光电转换效率. 关键词： 有机太阳能电池 体异质结 梯度掺杂     

Superconductivity in Alkali-Doped C60

There ark three kinds of effective attractive interaction between C₆₀^2- and "nearly free" electron in A₃C₆₀: 1) the strong short-range attraction between the low energy unoccupied orbital of C₆₀^2- ions and the "nearly free" electrons; 2) the potential barrier due to large angular momentum of t_1u orbital; 3) the A⁺ crystal field forced "nearly free" electrons in C₆₀^2- neighborhood. All effective attraction coupling with the A⁺ optical modes and the vibration modes of C₆₀ mass center produces a strong electron-phonon interaction. It plays a principal role for A₃C₆₀ superconductivity. Based upon this mechanism critical temperature and other properties of superconductivity state can be explained by means of the BCS theory.     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于sp³杂化C-H键的对称伸缩振动和反对称伸缩振动的红外特征峰2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.     

溶剂对钙钛矿薄膜形貌和结晶性的影响研究

溶剂对钙钛矿太阳能电池器件有着至关重要的影响. 基于目前常用的N, N-二甲基甲酰胺(DMF)和丁内酯(GBL)溶剂, 一步溶液旋涂技术和介孔电池结构, 制备的钙钛矿薄膜的形貌、结晶性, 以及最终的器件光电转化效率存在较大的差异, 利用DMF作为溶剂, 效率仅为2.8%, 而基于GBL的电池效率可以达到10.1%. 结合SEM, HRTEM, XRD和UV等表征手段, 分析了钙钛矿从DMF溶液和GBL溶液中结晶析出的不同机理, 明确了溶剂跟PbI₂的配位作用对钙钛矿的溶解、析出过程的制约作用, 揭示了造成器件效率差异的本质原因.     

Structural properties of C60 in solution

In this paper SANS results on C₆₀ solutions are presented. The data analysis allows to determine the value of the gyration radius of C₆₀ dissolved in CS₂, a solvent capable to guarantee a good contrast for the neutron probe. The study indicates that the gyration radius R_g is independent of concentration.     

Metallic Rb4C60 and Rb5C60 on the top layer of C60 single crystal

Photoemission studies reveal the existences of metallic Rb₄C₆₀ and Rb₅C₆₀ surface phases on the top layer of C₆₀ single crystal. After Rb₃C₆₀ thin film with thickness of nanometers has formed on the (1 1 1) surface layers of the C₆₀ single crystal, the excess deposition of Rb atoms do not induce the bulk-like face-centered cubic to body-centered tetragonal or body-centered cubic structure transitions at room temperature. The large size of C₆₀ molecule offers the surface vacancies for the formation of Rb₄C₆₀ and Rb₅C₆₀ monolayer that is further verified by Rb 3d core-level photoemission measurements. Valence band photoemission results exhibit the surface phases are metallic.     

钾掺杂对三联苯的超导特性探寻

新型超导材料的设计合成及其超导机理的探索是目前凝聚态物理学领域的重要研究方向. 本文采用高真空热烧结方法制备了钾掺杂对三联苯粉末材料并表征了它们的晶体结构、分子振动、磁学及超导特性. X射线衍射图谱和拉曼光谱表明在烧结样品中除存在钾掺杂对三联苯和KH外, 还含有苯环重组的C₆₀和石墨成分. 拉曼光谱中部分峰位的红移进一步证实钾成功掺入对三联苯分子晶体中并将4 s电子转移到C原子上. 零场冷却磁性测量结果表明: 多数样品在整个温度测量区间表现为居里顺磁性, 但少数样品呈现出抗磁性, 而且在17.86, 10.00 和6.42 K三个温度点出现磁化率突降的反常行为, 其中17.86 K处的突降很可能源于钾掺杂C₆₀引起的超导转变, 而后两者可能与钾掺杂对三联苯导致的超导相关. 研究结果有助于理解金属掺杂芳香烃有机超导体这一新兴超导家族的晶体生长和物理特性, 同时也提供了一种低温制备C₆₀和石墨的新方法.     

SiC formation on Si(100) via C60 precursors

The interaction between C₆₀ molecules and the Si(100) surface and the preparation of silicon-carbide thin films by thermal reaction of C₆₀ molecules with the Si(100) surface have been investigated using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, reflection high-energy electron diffraction and atomic force microscopy measurements. The effects of annealing temperature and C₆₀ coverage on the SiC formation will be discussed. It is found that the C₆₀ molecules bond covalently with silicon, and the number of bonds increase upon increasing the annealing temperature. Annealing at T≥830°C entails the formation of stoichiometric silicon carbide clusters that coalesce to form a continuous SiC layer when the C₆₀ coverage is greater than one monolayer. Deep pits acting as silicon diffusion channels are present with dimensions that increase with the amounts of C₆₀.

The interaction of C₆₀ with the SiC surface was also investigated. It is found that a similar covalent interaction is present in the two systems C₆₀/Si and C₆₀/SiC.     

ELECTRONIC STRUCTURE STUDIES OF THE C60 FILM CONDENSED ON 2H-MoS2(0001) SURFACE

The electronic structure and vibrational spectrum of the C₆₀ film condensed on a 2H- MoS₂(0001) surface have been investigated by X-ray photoelectron spectroscopy (XPS), ul-traviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES) and infrared high-resolution electron-energy-loss spectroscopy (HREELS). AES analysis showed that at low energy side of the main transition, C₆₀ contains a total of three peaks just like that of graphite. However, the energy position of the KLL main Auger transition of C₆₀ looks like that of diamond, indicating that the hybridization of the carbon atoms in C₆₀ is not strictly in sp²- bonded state but that the curvature of the molecular surface introduces some sp²pz- bonded character into the molecular orbitals. XPS showed that the C 1s binding energy in C₆₀ was 285.0eV, and its main line was very symmetric and offered no indication of more than a single carbon species. In UPS measurement the valence band spectrum of C₆₀ within 10eV below the Fermi level (E_F) shows a very distinct five-band structure that character-izes the electronic structure of the C₆₀ molecule. HREEL results showed that the spectrum obtained from the C₆₀ film has very rich vibrational structure. At least, four distinct main loss peaks can be identified below 200 meV. The most intense loss was recorded at 66 meV, and relatively less intense losses were recorded at 95, 164 and 197meV at a primary energy of electron beam E_P = 2.0eV. The other energy-loss peaks at 46, 136, 157 and 186meV in HREEL spectrum are rather weak. These results have been compared to infrared spectrum data of the crystalline solid C₆₀ taken from recent literatures.     

富勒烯C20四聚体的结构与性能研究

采用密度泛函理论(DFT)中的杂化密度泛函(B3LYP)方法, 在6-31 G基组水平上对C₂₀四聚体进行了几何参数全优化, 得到了基态构型, 并对其稳定性、电子结构、极化率和芳香性进行了计算研究. 结果表明: C₂₀碳笼以[2+2]加成方式结合形成C₂₀四聚体, 具有良好的热力学稳定性; C原子内部以sp²的方式杂化, C原子之间有少量电荷转移; C₂₀ 四聚体的IR和Raman光谱都有较多的振动峰; 随碳笼数的增加, C₂₀聚合物中原子间的成键相互作用随之增强; C₂₀四聚体具有芳香性.     

胺草磷系列——晶Ⅰ和晶Ⅱ分子结构和晶体结构测定

胺草磷是一种合成除草剂,其晶体为无色片状,在无水乙醇和甲苯中能得到重新结晶。胺草磷晶Ⅰ和晶Ⅱ是胺草磷系列中的两个样品,均属于单斜晶系,空间群均为P2_{1/c,晶胞参数基本一样,aⅠ=8.575?,bⅠ=26.541?,cⅠ=7.063?,βⅠ=94.744°;aⅡ=8.575?,bⅡ=26.538?,cⅡ=7.073?,βⅡ=93.819°。分子粗结构模型均用直接法获得,并用全矩阵最小二乘法进行修正,最后RⅠ=0.10;RⅡ=0.11。结构中的苯环平面和硝基平面成垂直关系。晶Ⅱ比晶Ⅰ除草效果好。 关键词：}     

Rapid synthesis of novel flowerlike ZnO structures by thermolysis of zinc acetate

Novel flowerlike ZnO structures have been rapidly synthesized on (1 0 0)-Si substrates via thermolysis of zinc acetate in air ambient without any catalyst. The obtained ZnO products exhibit well-defined flowerlike morphologies consisting of multilayer petal crystals with tapering feature. High-resolution transmission electron microscope (HRTEM) and corresponding selected area electron diffraction pattern (SAED) reveal that these petal crystals are single crystal in nature and preferentially oriented in the c-axis direction. Room-temperature photoluminescence (PL) spectra show that all the samples exhibit prominent UV emissions around 376.8 nm and very weak visible emission peaks, which demonstrates that there are few deep-level defects in the single crystal petals of the flowerlike ZnO structures. The growth mechanism of the as-synthesized flowerlike ZnO structures was also discussed.     

Auger electron spectroscopy and electron energy loss spectroscopy studies on carbonization of Si(100) and (111) surfaces with ethylene

The reactions of Si(100) and Si(111) surfaces at 700 °C (973 K) with ethylene (C₂H₄) at a pressure of 1.3×10⁻⁴ Pa for various periods of time were studied by using Auger electron spectroscopy (AES) and electron energy loss spectroscopy (ELS). For a C₂H₄ exposure level, the amount of C on the (111) surface was larger than that on the (100) surface. The formation of β-SiC grain was deduced by comparing the C_KLL spectra from the sample subjected to various C₂H₄ exposure levels, and from β-SiC crystal.     

场发射显示器用蓝色YVO_4∶Tm~(3+)纳米荧光粉的制备及性能研究

采用溶剂热法成功地制备出了YVO4∶Tm3+纳米荧光粉,并用X射线衍射仪(XRD)、透射电子显微镜(TEM)、紫外分析仪、紫外可见(UV-Vis)吸收光谱和光致发光(PL)光谱对YVO4∶Tm3+纳米荧光粉进行测试和表征。实验结果表明,YVO4∶Tm3+纳米荧光粉可发出明亮的蓝光,色纯度和发光强度都很高,而且具有良好的热稳定性。因此,YVO4∶Tm3+纳米荧光粉是一种十分适用于场发射显示器的荧光粉。     

Co,Zn共掺铌酸锂电子结构和吸收光谱的第一性原理研究

利用基于密度泛函的第一性原理的计算方法,研究了Co单掺及Co和Zn共掺LiNbO_3晶体的电子结构和吸收光谱.研究显示,各掺杂体系铌酸锂晶体的带隙均较纯铌酸锂晶体变窄. Co:LiNbO_3晶体禁带宽度为3.32 eV; Co:Zn:LiNbO_3晶体, Zn的浓度低于阈值或达到阈值时,禁带宽度分别为2.87或2.75 eV. Co:LiNbO_3晶体在可见-近红外光波段2.40, 1.58, 1.10 eV处形成吸收峰,这些峰归结于Co 3d分裂轨道的跃迁;加入抗光折变离子Zn~(2+),在1.58, 1.10 eV处的吸收峰增强,可以认为Zn~(2+)与Co~(2+)之间存在电荷转移,使e_g轨道电子减少,但并不影响t_(2g)轨道电子.结果表明,晶体中的Co离子在不同共掺离子下可充当深能级中心(2.40 eV),或可充当浅能级中心(1.58 eV),两种情况下,掺入近阈值的Zn离子均有助于实现优化存储.     

Doublet luminescence due to coexistence of excitons and electron-hole plasmas in optically excited CH3NH3PbBr3 single crystal

Doublet luminescence from hybrid metal trihalide perovskite semiconductors is observed along with materials processing when high-quality single crystals are obtainable. Yet, the underlying physical mechanism remains poorly understood. Here, we report controllable solution-processed crystallization that affords high-quality CH₃NH₃PbBr₃ single crystals with atomically flat pristine surfaces. Front-face photoluminescence (PL) shows doublet luminescence components with variable relative intensities depending on the crystal surface conditions. We further find that the low-energy PL component with asymmetric spectral line-shape becomes predominant when the atomically flat crystal surfaces are passivated in the ion-abundant saturated solutions, while poor-quality single crystal with visually rough surface only gives the high-energy PL with symmetric line-shape. The asymmetric spectral line-shape of the low-energy PL matches perfectly with the simulated bandedge emission. Therefore, the low-energy PL component is attributable to the intrinsic bandedge emission from the crystal bulk while the high-energy one to surface-specific emission. Elliott fitting to the absorption data and multi-exponential fitting to the time-resolved photoluminescence traces jointly indicate the coexistence of excitons and electron-hole plasmas in optically excited CH₃NH₃PbBr₃ single crystals, thereby catching the physical merit that leads to the occurrence of doublet luminescence.