杀线威在Fe_3O_4/Ag纳米磁粒上的吸附及表面增强拉曼光谱研究

采用共沉淀法合成了Fe_3O_4磁性纳米颗粒,进一步以柠檬酸三钠还原法制备出了具有SERS活性的Fe_3O_4/Ag磁性包覆修饰材料,用紫外可见吸收光谱、能谱及透射电镜对结构与形貌进行表征,发现所制备的Fe_3O_4/Ag纳米材料粒径约为30~60nm,形貌规整接近球形,经测试Fe_3O_4/Ag材料很容易被磁铁收集,能够满足分散萃取再收集的需要。根据密度泛函理论(DFT)对杀线威(Oxamyl)、Oxamyl-Ag和OxamylAg4进行了理论结构优化计算,得到了杀线威的理论拉曼光谱和与Ag表面增强拉曼光谱及其谱峰的归属,结合表面增强拉曼光谱(SERS)测定,研究了杀线威在Fe_3O_4/Ag表面的吸附行为和增强效应,测算得到杀线威在Fe_3O_4/Ag表面上的增强因子为2.08×105。研究表明:理论计算的杀线威拉曼光谱与测定的拉曼光谱具有较好的一致性,DFT理论计算中发现研究分子与活性Ag原子作用越多,与实测值常规拉曼NRS越接近;杀线威以双键侧N原子和S原子与Fe_3O_4/Ag表面吸附作用为主;双键侧N优先与Ag吸附成键后,整个分子靠近Ag表面,最终使得双键侧N原子与S原子共同吸附在Ag表面;Fe_3O_4/Ag磁性纳米复合材料具有显著的富集吸附和拉曼增强作用;可利用其作为拉曼基底,以实现SERS光谱法对杀线威农残的快速分析检测。     

Raman study of NiFe2O4 nanoparticles,bulk and films: effect of laser power

Nanoparticles, bulk and thin films of NiFe₂ O₄ compounds are studied by micro‐Raman spectroscopy. The effect of varying the incident laser power up to 40 mW was studied in all forms of the samples. The spectra showed a large magnitude of red shift and line broadening as a result of high incident laser power. It is shown that the inverse spinel structure remains robust, and no trace of laser‐induced oxidation was observed. The low‐temperature study of the bulk and nanoparticles has also been carried out for elucidating thermal effects due to the high incident laser power. The rise in temperature for maximum incident laser power of 40 mW was estimated to be ∼625 °C. Copyright © 2010 John Wiley & Sons, Ltd.     

Bi4-xLaxTi3O12-SrBi4Ti4O15,共生结构铁电材料拉曼光谱研究

在常温下，对La掺杂共生结构铁电陶瓷Bi_4-xLa_xTi_3O_12-SrBi_4-yLayTi_4O_15［BLT-SBLT(x+y),x+y= 0.00, 0.25,0.50,0.75,1.00,1.25,1.50］进行了拉曼光谱研究.结果表明，在掺杂量低于0.50时，La只取代类钙钛矿层中的Bi，当掺杂 量高于0.50后，部分La开始进入(Bi_2O_2)^2+层. La取代(Bi_2O_2)^2+层中的部分Bi以后，(Bi_2O_2)^2+层结构发生变化 ，原有的绝缘层和空间电荷库的作用减弱，导致材料剩余极化下降. La掺杂量增至1.50时，样品出现弛豫铁电性，这与30cm^-1以下模的软化相对应，说明La掺杂可引起材料 的结构相变. 关键词： Bi4-xLaxTi3O12-SrBi4Ti4O15 La掺杂 声子模 拉曼频移     

Strain status of epitaxial Ge film on a Si (001) substrate

An epitaxial Ge film was grown on a Si (001) substrate via a two-step process through the molecular beam epitaxy technique. The strain status of non-annealed and annealed epitaxial Ge films was determined by X-ray diffraction, Raman spectroscopy, and a combination of high-resolution transmission electron microscopy and geometric phase analysis. Results showed that the strain in non-annealed and annealed epitaxial Ge films is nonhomogeneous from the Ge/Si interface to the Ge film surface. The strain parallel to the interface in the non-annealed epitaxial Ge film is compressive; this strain reaches a minimum near the surface and a maximum at the interface. By contrast, the strain parallel to the interface in the annealed epitaxial Ge film is tensile; this strain reaches a minimum at the interface and a maximum near the surface.     

Fe3O4@Au纳米材料的制备和光谱性质

采用共沉淀法制备了Fe3O4纳米颗粒,并以其为晶种利用晶种生长法制备了Fe3O4@Au磁性复合纳米粒子。吸收光谱显示Au壳层成功包覆在了Fe3O4纳米核的表面。以结晶紫为探针分子的表面增强拉曼散射（SERS）光谱展示了Fe3O4@Au良好的SERS活性。     

表面吸附K原子的多层FeSe/SrTiO3(001)薄膜的抗磁响应的原位测量

SrTiO₃（001）单晶表面上生长的单层FeSe薄膜显示出了超乎寻常的高温超导电性,其超导增强机制的一个重要因素是电子由衬底转移到了单层FeSe薄膜当中.基于此认识,研究者们在吸附了钾（K）原子的多层FeSe薄膜表面上观察到了类似超导能隙的隧穿能谱和光电子能谱.但这种自上而下的电子掺入方式在多层FeSe薄膜表面上可能引起的高温超导电性,还缺乏零电阻或迈斯纳效应等物性测量实验的直接证实.本研究利用自行研制的一台特殊的多功能扫描隧道显微镜,在生长于SrTiO₃（001）衬底上的多层FeSe薄膜表面上,不但观察到了超导能隙随K吸附量的变化,而且利用原位双线圈互感测量技术,成功地的观察到了该薄膜的抗磁响应,并由此确定了该薄膜样品呈现迈斯纳效应的超导转变温度为23.9 K.其穿透深度随温度的变化呈二次幂指数关系,表明该体系的超导序参量很可能具有S^±配对对称性.     

Structural and magnetic properties of ultrathin epitaxial Fe films on GaAs(001) and related semiconductor substrates

This article presents a review of the structural and magnetic properties of ultrathin epitaxial Fe films on GaAs(001) and related semiconductor substrates. Interest in these systems and Fe/GaAs(001) in particular has increased significantly over the last two decades, largely due to the emergence of the field of magnetoelectronics. Since then numerous studies of molecular beam epitaxy of Fe on GaAs(001) have been carried out, making it by far the best researched Fe/semiconductor(001) system. Issues such as magnetic anisotropy in the ultrathin regime, however, remain controversial with contradictory reports in the literature giving rise to considerable controversy within the field. By carefully scrutinizing the enormous amount of literature published on Fe/GaAs(001) so far and analysing these results within the wider context of Fe/semiconductor(001) systems, this article tries to settle some of these controversial issues, hence providing a long overdue ‘common denominator' for research in this area.     

原位氧化水解法制备网状结构Fe3O4薄膜

在壳聚糖膜上通过原位氧化水解反应制备了网状结构的Fe3O4薄膜.采用X射线衍射、扫描电子显微镜和热重差热分析对产物进行了分析和表征,结果表明,所制备的Fe3O4膜为纯相反尖晶石结构;网孔直径大约50～300nm,网壁厚度大约30nm;Fe3O4转化为γFe2O3的温度约为458℃.     

Fe3O4/MgO(100)薄膜外场诱导电阻变化特性

采用激光分子束外延（L-MBE）方法,以MgO(100)为基底生长了Fe3O4单晶薄膜, 研究了Fe3O4/MgO(100)薄膜外场（温度、磁和激光场）诱导电阻变化特性。X射线衍射(XRD)分析表明Fe3O4薄膜是沿MgO(200)晶面外延生长的单晶薄膜;反射高能电子衍射（RHEED）强度振荡曲线分析表明Fe3O4薄膜表面平整,而且生长模式为2维层状生长;原子力显微镜（AFM）分析表明Fe3O4薄膜表面粗糙度为0.201 nm,说明薄膜表面达到原子级平整度。外场作用下Fe3O4薄膜的电阻测试表明:薄膜样品的电阻在120 K(Verwey转变温度)出现一峰值,略微下降后继续增大, 展现出半导体型的导电特性; 在激光作用下,整个测量温度范围内薄膜样品的电阻减小,样品展示出瞬间光电导的特性;从降温曲线可以看出, Verwey转变温度由无激光作用时的120 K上升到有激光作用时的140 K; 光致电阻变化率随着温度的降低而增大,这主要是由于激光作用导致电荷有序态的退局域化。     

Bi4-xLax Ti3O12-SrBi4-y Lay Ti4O15共生结构铁电材料拉曼光谱研究

在常温下 ,对La掺杂共生结构铁电陶瓷Bi4 -xLaxTi3O1 2 _SrBi4 -yLayTi4 O1 5[BLT_SBLT(x y) ,x y =0 0 0 ,0 2 5 ,0 5 0 ,0 75 ,1 0 0 ,1 2 5 ,1 5 0 ]进行了拉曼光谱研究 .结果表明 ,在掺杂量低于 0 5 0时 ,La只取代类钙钛矿层中的Bi,当掺杂量高于 0 5 0后 ,部分La开始进入 (Bi2 O2 ) 2 层 .La取代 (Bi2 O2 ) 2 层中的部分Bi以后 ,(Bi2 O2 ) 2 层结构发生变化 ,原有的绝缘层和空间电荷库的作用减弱 ,导致材料剩余极化下降 .La掺杂量增至 1 5 0时 ,样品出现弛豫铁电性 ,这与 30cm- 1 以下模的软化相对应 ,说明La掺杂可引起材料的结构相变     

Verwey相变处Fe3O4的结构、磁性和电输运特性

作为典型的金属–绝缘体转变,Fe3O4的Verwey相变蕴涵的丰富物理现象与微观机制,因而受到了人们的广泛关注.在Verwey相变处,Fe3O4的晶体结构、电子结构以及磁各向异性等均发生转变,但其磁基态并未发生改变.与其他强关联体系相比,Fe3O4的Verwey相变不需要考虑磁交换耦合作用的变化,有利于揭示强关联体系中金属–绝缘体转变的物理本质.本文从晶体结构、电荷有序、电输运特性、磁性和铁电特性等方面简要地介绍了Fe3O4的Verwey相变的研究历史和现状.     

(Bi, La)4Ti3O12-Sr(Bi, La)4Ti4O15共生结构铁电材料性能研究

采用固相烧结工艺,制备了不同La掺杂量(x=0.00,0.25,0.50,0.75,1.00,1.25和1.50)的(Bi, La)4Ti3O12-Sr(Bi, La)4Ti4O15 (SrBi8-xLaxTi7O27)共生结构铁电陶瓷样品.用x射线衍射对其进行微结构分析,并测量铁电、介电性能.结果发现,La掺杂未改变Bi4Ti3O12-SrBi4Ti4O15共生结构铁电材料的晶体结构.随掺杂量的增加,样品的矫顽场(Ec)略有增加,剩余极化(2Pr)先增大,后减小.在x＝0.50时,2Pr达到极大值,为25.6 μC*cm-2,与Bi4Ti3O12-SrBi4Ti4O15相比,2Pr增加了近60%,而Ec仅增加约10%.随La掺杂量的增加,样品的居里温度TC逐渐降低,x＝0.50时,TC=556 ℃.在x=1.50时,样品出现弛豫铁电体的典型特征.     

Surface‐enhanced Raman scattering of 4‐mercaptopyridine on sub‐monolayers of α‐Fe2O3 nanocrystals (sphere,spindle, cube)

We report surface‐enhanced Raman scattering (SERS) spectra from 4‐mercaptopyridine (4‐Mpy) adsorbed on sub‐monolayers of α‐Fe₂O₃ nanocrystals (sphere, spindle, cube). The maximum enhancement factor has been estimated to be about 10⁴ compared to that of 4‐Mpy in solution. A possible mechanism has been proposed that the charge transfer between the α‐Fe₂O₃ nanocrystals and the 4‐Mpy molecules is most likely responsible for the observed enhancement of Raman intensity of adsorbed 4‐Mpy molecules as surface plasmon resonances have not occurred. Copyright © 2009 John Wiley & Sons, Ltd.     

纳米Fe3O4磁性液体稳定性的研究

从理论上解析了磁性颗粒之间的相互作用对纳米磁性液体稳定性的影响 ,指出磁粒半径和浓度 ,表面活性剂的包覆是影响磁液稳定性的重要因素 .采用湿化学共沉淀法制备了纳米Fe3O4 磁性液体 ,经过TEM等手段的表征 ,证明平均粒径为 10nm ,稳定性良好 .实验研究了加料方式、搅拌速度、分散作用、表面活性剂包覆时机、包覆时间和加入量以及pH值诸多工艺因素对磁液稳定性的影响 ,并分析了这些因素的影响机制     

磁响应Fe_3O_4@PS胶体光子晶体的制备及性能研究

本文首先通过共沉淀法制备油酸修饰的磁性Fe_3O_4纳米粒子,并将其均匀分散于正辛烷中得到磁流体,然后利用一步细乳液聚合法合成了单分散Fe_3O_4@PS磁性微球。扫描电镜分析结果表明,Fe_3O_4的粒径在13nm左右,所形成的Fe_3O_4@PS微球的粒径在120~150nm左右;VSM测试结果显示所合成的Fe_3O_4@PS微球具有超顺磁性,其饱和磁化强度约为25emu/g;Fe_3O_4@PS微球表面携带明显的负电荷,其表面Zeta电势为-60mV。反射光谱测试结果表明,Fe_3O_4@PS分散于水中形成的胶体溶液在磁场作用下呈现出明亮的结构色,具有明显的带隙特征;随着磁场强度的变化,反射峰波长可在450~650nm进行调谐。     

Fe_3O_4@SiO_2@TiO_2复合纳米结构的尺寸与磁性调控

采用共沉淀法和溶剂热法制备了不同尺寸的Fe_3O_4纳米粒子,通过Stber法和溶胶-凝胶法在Fe_3O_4磁核上包覆SiO_2和Ti O2壳层获得不同尺寸的Fe_3O_4@SiO_2@Ti O2复合纳米结构.采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和振动样品磁强计(VSM)等对其结构、形貌和磁性进行了研究.结果表明,大尺寸复合纳米粒子包覆均匀,分散性好,饱和磁化强度较大,有利于TiO_2光催化剂的磁回收与再利用.     

新型螯合磁性纳米Fe_3O_4的制备及其性能研究

采用共沉淀法制备了磁性四氧化三铁(Fe3O4)纳米粒子,并通过硅烷偶联剂对其表面进行改性,进一步在其表面偶联修饰氨基硫脲,制备了螯合磁性纳米Fe3O4粒子。利用广角X射线衍射仪(WAXD)、红外光谱仪(FTIR)、分光光度计等对磁性纳米粒子的结构和性能进行了表征。结果表明,纳米Fe3O4为反尖晶石结构,通过偶联修饰可以实现氨基硫脲在纳米粒子表面的化学改性。螯合磁性纳米粒子具有良好的分散性和磁响应性,且对多种金属离子(Pb2+、Hg2+、Zn2+、Cd2+)具有良好的螯合效果。     

Fe3O4@SiO2@TiO2复合纳米结构的尺寸与磁性调控

采用共沉淀法和溶剂热法制备了不同尺寸的Fe3O4纳米粒子,通过Stöber法和溶胶-凝胶法在Fe3O4磁核上包覆SiO2和TiO2壳层获得不同尺寸的Fe3O4@SiO2@TiO2复合纳米结构．采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和振动样品磁强计(VSM)等对其结构、形貌和磁性进行了研究．结果表明,大尺寸复合纳米粒子包覆均匀,分散性好,饱和磁化强度较大,有利于TiO2光催化剂的磁回收与再利用．     

High-temperature Raman spectroscopic study of vanadoborate Na_3VO_2B_6O_(11)

Raman spectra of a vanadoborate(Na3VO2B6O11) crystal from room temperature up to the melting point have been recorded. The main internal vibrational modes of the crystal have been assigned. It was found that all the Raman bands exhibit decreases in frequency and the widths of the Raman bands increase with the increase of temperature. However,no phase transition was observed under 525℃. The micro-structure of its melt was studied by quantum chemistry ab initio calculation. The continuous three-dimensional network of the crystal collapsed and transformed into VO_4 and VBO_6 clusters during the melting process with an isomerization reaction from four-coordinated boron to a three-coordinated species.