利用扫描隧道显微镜在溶液中直接观测过渡族金属硫属化合物（英文）

本文利用自制的溶液扫描隧道显微镜在溶液环境下直接观测到TiSe2、MoTe_2和TaS_2样品的原子分辨率图像.通过将单晶样品在溶液中直接解理,可以保护解理过的新鲜样品表面在几个小时内不会被严重污染.利用自行搭建的溶液扫描隧道显微镜,首先观察到了TiSe2活泼样品的原子分辨率图像,并观察到了TiSe2表面所特有的点缺陷和三角形缺陷结构.此外,还观察到了MoTe2的原子分辨率超结构和TaS2表面的电荷密度波结构.结果表明:在室温、溶液环境下能更高效的研究过渡族金属硫属化合物等活泼样品的表面电子态结构,同样适用于溶液环境下的电催化和电化学研究.     

扫描隧道显微镜

 １９８２年,Ｂｉｎｎｉｎｇ和Ｒｏｈｒｅｒ研制成世界上第一台扫描隧道显微镜ＳＴＭ（ＳｃａｎｎｉｎｇＴｕｎｅｌｉｎｇＭｉｃｒｏｓｃｏｐｅ）,是目前唯一具有原子级分辨率的实空间成像技术,当这两位科学家用ＳＴＭ观察到高序石墨表面原子的图像时,人们对微观世界的认识一下子从幻想和抽象的分析飞跃到对原子的直接观察和操纵．ＳＴＭ和其它的传统显微镜相比,光学显微镜、扫描电子显微镜的分辨率不够,而高分辨的透射电子显微镜虽然能够达到较高的分辨率,可它的制样异常麻烦,破坏了样品,而且在测量过程中离不开真空环境．ＳＴＭ因其可直接观察物体表面原子结构而不会对样品表面造成任何损伤.     

CO和O2分子与TiO2(110)表面负载Pt单原子的相互作用

Pt单原子在低温CO氧化反应中具有很高的催化活性. 利用扫描隧道显微术与密度泛函理论,研究了Pt单原子在还原性TiO₂(110)表面的吸附行为及其与CO和O₂分子的相互作用. 研究发现在80 K低温下,TiO₂表面的氧空位缺陷是Pt单原子的最优吸附位. 将CO和O₂分子分别通入Pt单原子吸附后的TiO₂表面,研究相应的吸附构型. 实验表明在低覆盖度下,单个Pt原子会俘获一个CO分子,CO分子同时与表面次近邻的五配位Ti原子(Ti_5c)成键,进而形成非对称的Pt-CO 复合物构型. 将样品从80 K升温到100 K后,TiO₂表面的CO分子会迁移到Pt-CO处形成Pt-(CO)₂的复合结构. 对于O₂分子,单个Pt原子同样会吸附一个O₂分子,O₂分子也会与最近邻或次近邻的Ti_5c原子成键形成两种Pt-O₂构型. 这些结果在单分子尺度上揭示了CO和O₂与Pt单原子的相互作用,呈现了CO与O₂反应中的初始状态.     

高稳定电化学扫描隧道显微镜研制

展示了一台自制的电化学扫描隧道显微镜. 这台电化学STM具有很高的稳定性,它在XY平面和Z方向的漂移速率分别为每分钟67和55.6 pm/min. 另外,特殊设计的扫描管部件有效地避免了在高湿度的环境中大漏电电流的产生. 详细描述了这台电化学STM的机械结构.通过在硫酸铜溶液中测量STM图像证明这套系统的优异性能,得到了大范围干净有序的Au(111)表面和高分辨的高聚石墨原子图像.     

简单紧凑高刚性扫描隧道显微镜的研制

本文展示了一台自主研制的扫描隧道显微镜,它的主要特色是利用了一个内壁抛光的蓝宝石导向管作为扫描头的导轨,从而形成了较短的探针到样品的机械回路. 该导向管里面是一个被弹簧片夹持的方形滑杆,而压电扫描头安装在该滑杆上使得扫描隧道显微镜本身结构比较简单、紧凑、刚性. 同时蓝宝石良好的热导率又有利于提高显微镜的热稳定性. 为了证明该扫描隧道显微镜的性能,本文给出了高质量的石墨原子分辨率图像.     

在Au(111)表面酞菁单分子与钴原子可控金属化反应

本文利用低温扫描隧道显微术和第一性原理计算研究了吸附在Au(111)表面的酞菁分子(H₂Pc)与Co原子在单分子水平上的金属化反应过程. 通过扫描探针的操纵手段,以可控的方式原位实现了单个H₂Pc分子与钴原子反应生成CoPc的金属化酞菁产物,揭示出源于H₂Pc和Co原子的π-d相互作用的中间过程. 结合第一性原理计算和中间产物的图像模拟,进一步阐明了这一氧化还原反应中成键和断键的关键机制,即脱氢和金属化过程并非由Co原子和吡咯环的H作用所致,而与Co原子和吡咯环上的N原子之间的作用有关.     

简单紧凑高刚性扫描隧道显微镜的研制（英文）

本文展示了一台自主研制的扫描隧道显微镜,它的主要特色是利用了一个内壁抛光的蓝宝石导向管作为扫描头的导轨,从而形成了较短的探针到样品的机械回路.该导向管里面是一个被弹簧片夹持的方形滑杆,而压电扫描头安装在该滑杆上使得扫描隧道显微镜本身结构比较简单、紧凑、刚性.同时蓝宝石良好的热导率又有利于提高显微镜的热稳定性.为了证明该扫描隧道显微镜的性能,本文给出了高质量的石墨原子分辨率图像.     

铜箔上生长的六角氮化硼薄膜的扫描隧道显微镜研究

利用扫描隧道显微镜研究了采用化学气相沉积法在铜箔表面生长出的高质量的六角氮化硼薄膜. 大范围的扫描隧道显微镜图像显示出该薄膜具有原子级平整的表面, 而扫描隧道谱则显示, 扫描隧道显微镜图像反映出的是该薄膜样品的隧穿势垒空间分布. 极低偏压的扫描隧道显微镜图像呈现了氮化硼薄膜表面的六角蜂窝周期性原子排列, 而高偏压的扫描隧道显微镜图像则呈现出无序和有序排列区域共存的电子调制图案. 该调制图案并非源于氮化硼薄膜和铜箔衬底的面内晶格失配, 而极有可能来源于两者界面处的氢、硼和/或氮原子在铜箔表面的吸附所导致的隧穿势垒的局域空间分布.     

石墨单晶表面原子的扫描隧道显微象

扫描隧道显微镜(STM)是近几年发展起来的一种直接观察物质表面微观结构的仪器.利用量子隧道效应,将极细的金属针尖接近样品表面扫描,从而获得样品表面的三维图象,可以反映表面原子排列和原子形态.图1是我们设计制造的扫描隧道显微镜原理图.采用压电陶瓷管P作为x,y和z方向的三维扫描器件.管表面等分为相邻90°的四个电极,针尖T固定在其中的一个电极上.尖端曲率半径为100nm左右的金属针尖,可用化学腐蚀法制备.两对电极上施加扫描电压时,针尖便在垂直于管轴z的x-y方向扫描,而z方向的高低变化则由加在内管壁上的电     

利用原位红外光谱与微分电化学质谱联用技术研究在Pt以及PtRu电极上发生的甲醇氧化反应

利用电化学衰减全反射原位傅里叶变换红外光谱与微分电化学质谱联用技术,在流动电解池环境以及恒电位条件下研究了Pt电极和Pt电极通过表面电沉积Ru形成的PtRu电极(Pt_xRu_y)上发生的甲醇氧化反应(反应电解质溶液为0.1 mol/L HClO₄+0.5 mol/L MeOH). 在0.3～0.6 V(参比电极为可逆氢参比)实验用到的所有电极上,CO是唯一能从红外光谱观察到的与甲醇相关的表面吸附物;在Pt_0.56Ru_0.44电极上可以观察到CO吸附在Ru原子形成的岛上和CO线式吸附在Pt电极表面红外波段,而其他电极上只能观察到Pt表面上线式吸附的CO;甲醇氧化活性按Pt_0.73Ru_0.27>Pt_0.56Ru_0.44>Pt_0.83Ru_0.17>Pt的顺序递减;在0.5 V 时,甲醇在Pt_0.73Ru_0.27电极上的氧化反应的CO₂电流效率达到了50%.     

Scanning tunnelling microscopy of charge-density waves in transition metal chalcogenides

We have used scanning tunnelling microscopes (STMs) operating at liquid helium and liquid nitrogen temperatures to image the charge-density waves (CDWs) in transition metal chalcogenides. The layer structure dichalcogenides TaSe₂, TaS₂, NbSe₂, VSe₂, TiSe₂ and TiS₂ have been studied including representative polytype phases such as 1T, 2H and 4Hb. Experimental results are presented for the complete range of CDW amplitudes and structures observed in these materials. In most cases both the CDW and the surface atomic structure have been simultaneously imaged. Results on the trichalcogenide NbSe₃ are also included.

The formation of the CDW along with the associated periodic lattice distortion gaps the Fermi surface (FS) and modifies the local density-of-states (LDOS) detected by the tunnelling process. The tunnelling microscopes have been operated mostly in the constant current mode which maps the LDOS at the position of the tunnelling tip. The relative amplitudes and profiles of the CDW superlattice and the atomic lattice have been measured and confirm on an atomic scale the CDW structures predicted by X-ray, electron and neutron diffraction. The absolute STM deflections are larger than expected for the CDW induced modifications of the LDOS above the surface and possible enhancement mechanisms are reviewed.

In the 2H trigonal prismatic coordination phases the CDWs involve a relatively small charge transfer and the atomic structure dominates the STM images. In the 1T octahedral coordination phases the charge transfer is large and the CDW structure dominates the STM image with an anomalously large enhancement of the STM profile. Systematic comparison of the STM profiles with band structure and FS information is included.

In the case of the 4Hb mixed coordination phases at the lowest temperatures two nearly independent CDWs form in alternate sandwiches. STM studies on 4Hb crystals with both octahedral and trigonal prismatic surface sandwiches have been carried out. The STM scans detect the relative strengths of the two CDWs as well as the interactions between the two types of CDW structure.

The STM scans are also able to detect defects and domain structure in the CDW image. Several examples will be given demonstrating the potential of the STM to detect these local variations in LDOS on an atomic scale. In contrast to the layer structure crystals the linear chain compound NbSe₃ shows a complex surface atomic structure as well as the formation of two CDWs. The surface atomic structure is resolved in the STM scans and profiles have detected the presence of the CDW modulation at 77K and 4.2K. These results demonstrate the feasibility of detecting CDW structure in the presence of complex atomic structure and using materials where dynamical CDW effects can also be studied by STM.

The range of STM results presented here show that the STM scans are extremely sensitive to the detail of the CDW structure and its effect on the LDOS. Although much of this structure has been deduced from diffraction studies, the ability to examine the CDW structure on an atomic scale with the STM is new. The sensitivity of the STM method suggests potential applications to a wide range of electronic structures in materials.     

Reflectivity studies of Ti- and Ta-dichalcogenides: Phonons

The i.r.-spectra of the 1T phases of TiS₂, TiSe₂, TaS₂ and TaSe₂ reveal features attributed to large free carrier densities and to i.r.-active longwavelength phonons. We find a single phonon in TiS₂, TiSe₂ and TaS₂, but six phonons in TaSe₂, The oscillator strengths are significantly higher in the Ti-compounds yielding large values of the infrared effective charge, ～6e, and electron-phonon coupling constant, 0.4–1.0. The observation of many modes in TaSe₂ is attributed to a superlattice distortion driven by a charge density wave.     

Diffusion of silver in TiSe2 single crystals

Diffusion of deposited silver through the surface of TiSe₂ single crystals has been investigated. It is found that diffusion occurs only near lattice defects. The X-ray photoelectron spectra of TiSe₂ single crystals with in situ deposited silver have been studied. It is found that, upon annealing in the spectrometer chamber, silver does not form chemical bonds with the host lattice. Original Russian Text ? A.I. Merentsov, E.A. Titova, P.E. Panfilov, S.N. Shamin, A.M. Ionov, A.N. Chaika, 2009, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2009, Vol. 73, No. 4, pp. 566–568. The paper was reported at the International Simposium.     

Organic superconductors revisited

The surfaces of a ten years aged crystal and a freshly prepared κ-(BEDT-TTF)₂Cu(NCS)₂ crystal were compared by scanning tunneling microscopy (STM). The molecularly-resolved STM images of the bc plane of the crystals agree with each other and with the electronic contrast obtained by new density functional theory (DFT) based simulations. Even after ten years STM images of the molecular stacking of BEDT-TTF display a variation in brightness at the positions of different molecules. We attribute this symmetry breaking concerning the brightness in the STM images of the otherwise equivalent BEDT-TTF dimers to the electronic states of a relaxed surface.     

Syntheses and characterization of polymer/TaS2 layered nanocomposites

Polymer/TaS₂ layered nanocomposites have been synthesized using the exfoliation–adsorption technique, using 1T-TaS₂, 2H-TaS₂, and 4Hb-TaS₂ single crystals hosts and poly(ethylene oxide) (PEO) and poly(ethylenimine) (PEI) as guest intercalates. Optimum conditions to synthesize nanocomposites were obtained for each set of TaS₂ polytypes and polymers using powder X-ray diffraction (XRD). XRD patterns showed that all nanocomposite materials contain polymer between all individual TaS₂ sheets. Although 1T-, 2H-, and 4Hb-TaS₂ polytypes are well known to show quite different temperature dependences of resistivity, the resistivities of all nanocomposites show similar temperature dependences.     

Superconductivity and single crystal growth of Ni0.05TaS2

Superconductivity was discovered in a Ni_0.05TaS₂ single crystal. A Ni_0.05TaS₂ single crystal was successfully grown via the NaCl/KCl flux method. The obtained lattice constant $c$ of Ni_0.05TaS₂ is 1.1999 nm, which is significantly smaller than that of 2H–TaS₂ (1.208 nm). Electrical resistivity and magnetization measurements reveal that the superconductivity transition temperature of Ni_0.05TaS₂ is enhanced from 0.8 K (2H–TaS₂) to 3.9 K. The charge-density-wave transition of the matrix compound 2H–TaS₂ is suppressed in Ni_0.05TaS₂. The success of Ni_0.05TaS₂ single crystal growth via a NaCl/KCl flux demonstrates that NaCl/KCl flux method will be a feasible method for single crystal growth of the layered transition metal dichalcogenides.     

Growth of textured nonstoichiometric MoTe2 films from Mo/Te layers and their use as precursor in the synthesis of MoTe2−xSx films

Molybdenum ditelluride, MoTe₂, thin films have been prepared on a glass substrate by depositing first a layer of Mo of 1 μm thickness by rf sputtering and then layers of tellurium of 4 μm thickness followed by annealing, in a vacuum sealed Pyrex tube, at 823 K for one hour. The films have been studied by X-ray diffraction, electron microprobe analysis, scanning electron microscopy and for optical and electrical properties. This indicated that the films so prepared are well crystallized and textured with a hexagonal structure similar to 2H-MoS₂. However, the film is non stoichiometric due to the presence of small amounts of oxygen. The optical properties are in good agreement with those of single crystals and film deposited by other means. The room temperature conductivity is of the same order of magnitude as that of single crystals. Finally, MoTe₂ has been used as a precursor for the growth of MoTe_2−xS_x films.     

On the nature of state with a charge-density wave in TiSe<Subscript>2</Subscript> from data of scanning tunneling microscopy

The surface of a fresh cleavage of TiS₂, TiSe₂, and TiTe₂ crystals has been investigated using scanning tunneling microscopy with atomic resolution. All materials are characterized by triangular defects coinciding in shape with those supposedly formed as a result of the local change in the titanium atom coordination from octahedral to trigonal-prismatic by the chalcogen due to the Jahn-Teller effect. The conclusion has been drawn that the Jahn-Teller effect exists in these materials, but it is responsible for the formation of nanodefects rather than for the transition to a charge-density wave state. It has been shown that this interpretation of defects allows one to understand the evolution of the stability boundary of a charge-density wave upon donor and acceptor doping.     

SrTiO3(0 0 1) reconstructions: the (2 × 2) to c(4 × 4) transition

Scanning tunneling microscopy (STM) is used to investigate the (0 0 1) surface structure of Nb doped SrTiO₃ single crystals annealed in ultra high vacuum (UHV). Atomically resolved images of the (2 × 2) reconstructed surface are obtained after annealing a chemically etched sample. With further annealing dotted row domains appear, which coexist with the (2 × 2) reconstruction. The expansion of these domains with further annealing gives rise to the formation of a TiO₂ enriched c(4 × 4) reconstruction.     

One-dimensional electronic order in underdoped surface of YBa2Cu3Oy studied by STM

We have performed low-temperature scanning tunneling microscopy (STM) experiments on the cold-cleaved surface of YBa₂Cu₃O_y single crystals to study the nanoscale electronic order in high-T_c superconductors. STM images measured at low-bias voltage below ∼50 meV show the one-dimensional (1D) electronic modulation along the Cu-O bonds (parallel to the b-axis). The 1D electronic modulation does not have long-range order and the periodicity along the a-axis varies within the range ∼2a-4a depending on the position on the surface, indicating the glassy electronic order in the underdoped CuO₂ plane.