n型Bi2Te3-ySey温差电材料薄膜的电化学制备及表征

采用电化学控电位的方法在不锈钢基片上电沉积制备了Bi₂Te_3-ySe_y温差电材料薄膜。研究了电沉积溶液中硒含量与薄膜中硒含量的关系，考察了不同沉积电位对电沉积Bi₂Te_3-ySe_y薄膜的温差电性能的影响，并采用ESEM、EDS、XRD等方法对电沉积薄膜的形貌、成分及结构进行了分析。结果表明，在含有Bi³⁺、HTeO₂⁺和Se⁴⁺的电沉积溶液中，采用电化学沉积的方法，可实现铋、碲、硒三元共沉积，生成Bi₂Te_3-ySe_y半导体化合物。改变电沉积溶液组成，可控制Bi₂Te_3-ySe_y化合物中硒的掺杂浓度。-0.04 V沉积电位下制备的Bi₂Te_3-ySe_y薄膜较平整、致密，组成为Bi₂Te_2.7Se_0.3。退火处理可提高电沉积Bi₂Te_3-ySe_y薄膜的塞贝克系数，且控制沉积电位为-0.04 V下制备的Bi₂Te_3-ySe_y薄膜退火后的塞贝克系数为-123 μV·K^-1。     

纳米结构Bi2Te3化合物的低温湿化学合成

通过对溶液pH值和颜色以及粉末结构的原位分析, 研究了低温湿化学Bi₂Te₃纳米粉末合成过程中的化学和物理反应机制. 结果表明, 碱性添加剂对合成Bi₂Te₃是必要的. 采用65 ℃低温湿化学合成方法, 在添加乙二胺四乙酸二钠(EDTA)的情况下, 制备了Bi₂Te₃纳米囊. 高分辨电镜观察表明, 这种内空管状结构纳米囊的壁厚约为6 nm.     

纳米结构Bi2Te3化合物的低温湿化学合成

通过对溶液pH值和颜色以及粉末结构的原位分析, 研究了低温湿化学Bi₂Te₃纳米粉末合成过程中的化学和物理反应机制. 结果表明, 碱性添加剂对合成Bi₂Te₃是必要的. 采用65 ℃低温湿化学合成方法, 在添加乙二胺四乙酸二钠(EDTA)的情况下, 制备了Bi₂Te₃纳米囊. 高分辨电镜观察表明, 这种内空管状结构纳米囊的壁厚约为6 nm.     

Bi2S3量子点敏化TiO2纳米阵列结构的制备及光电性能研究

利用水热法制备一维TiO₂纳米棒阵列,并采用化学浴沉积法(CBD)结合自组装技术在TiO₂纳米棒上敏化Bi₂S₃量子点,形成TiO₂/Bi₂S₃复合纳米棒阵列.系统研究了复合结构的表面形貌、晶体结构、光学及光电性能.结果表明:在修饰有三氨丙基三乙氧基硅烷自组装单分子膜(APTS-SAMs)的TiO₂纳米棒表面形成一层致密的Bi₂S₃量子点敏化层,这一技术的关键是含-NH₂末端的APTS-SAMs可有效促进Bi₂S₃的异相成核作用;Bi₂S₃的沉积时间对复合结构的光吸收及光电响应性能有决定性的影响,薄膜的光电流随着沉积时间呈先增加后减小的趋势,在沉积时间为20 min时,光电流密度最大.这是因为随着沉积时间的增加,TiO₂纳米棒表面Bi₂S₃量子点密度增大,光吸收增加;而当沉积时间进一步延长时,Bi₂S₃在TiO₂纳米棒表面的大量负载而形成堆积和团聚,导致表面缺陷增多,光生电子复合几率增大,从而使光电流密度减小.     

Bi2S3量子点敏化TiO2纳米阵列结构的制备及光电性能

利用水热法制备一维TiO₂纳米棒阵列,并采用化学浴沉积法(CBD)结合自组装技术在TiO₂纳米棒上敏化Bi₂S₃量子点,形成TiO₂/Bi₂S₃复合纳米棒阵列。系统研究了复合结构的表面形貌、晶体结构、光学及光电性能。结果表明:在修饰有三氨丙基三乙氧基硅烷自组装单分子膜(APTS-SAMs)的TiO₂纳米棒表面形成一层致密的Bi₂S₃量子点敏化层,这一技术的关键是含-NH₂末端的APTS-SAMs可有效促进Bi₂S₃的异相成核作用;Bi₂S₃的沉积时间对复合结构的光吸收及光电响应性能有决定性的影响,薄膜的光电流随着沉积时间呈先增加后减小的趋势,在沉积时间为20min时,光电流密度最大。这是因为随着沉积时间的增加,TiO₂纳米棒表面Bi₂S₃量子点密度增大,光吸收增加;而当沉积时间进一步延长时,Bi₂S₃在TiO₂纳米棒表面的大量负载而形成堆积和团聚,导致表面缺陷增多,光生电子复合几率增大,从而使光电流密度减小。     

从理论模型到探究应用：二维材料锡烯的发展史

2011年,中科院物理研究所的姚裕贵教授从理论上对二维锡进行了研究,首次预测了二维锡是一种拓扑绝缘体。至2013年,二维锡的理论研究已较为成熟,美国斯坦福大学的张首晟教授基于锡的拉丁文stannum和二维烯材料2D-Xene后缀组合正式提出了锡烯(Stanene)的概念。2015年,上海交通大学的贾金锋教授等人利用分子束外延技术在Bi₂Te₃(111)衬底上首次成功地生长出了二维锡烯。随后,锡烯在不同衬底上相继生成,其制备方法取得了一定的进展。人们也在制备探究中逐渐发现,锡烯具有优异的物化性质,在众多领域内有良好的应用前景。锡烯的发展史重新诠释了二维材料的发展机制,为新型二维材料的预测、制备与应用提供了新的视角和思路。     

基于第一性原理的无铅无机钙钛矿Cs3Bi2X9(X=Cl、Br、I)光电性能表面效应研究

用基于第一性原理的密度泛函理论方法,对Cs₃Bi₂X₉（X=Cl、Br、I）的光电特性进行理论计算,并系统阐述这3种晶体的表面效应对光电性能的影响。结果表明,3种材料的光学特性由铋原子和卤素原子最外层p轨道上的价电子主导。在可见光区中,材料的吸收峰会随卤素原子序数的增加呈现红移,其中一维结构的Cs₃Bi₂Cl₉表面结构在光吸收能力上尤为特别且敏感;二维结构的Cs₃Bi₂Br₉光吸收能力会受厚度影响;零维结构的Cs₃Bi₂I₉非常稳定,且几乎不受表面特性和晶体厚度的影响。     

基于第一性原理的无铅无机钙钛矿Cs3Bi2X9(X=Cl、Br、I)光电性能表面效应研究

用基于第一性原理的密度泛函理论方法,对Cs₃Bi₂X₉(X=Cl、Br、I)的光电特性进行理论计算,并系统阐述这3种晶体的表面效应对光电性能的影响。结果表明,3种材料的光学特性由铋原子和卤素原子最外层p轨道上的价电子主导。在可见光区中,材料的吸收峰会随卤素原子序数的增加呈现红移,其中一维结构的Cs₃Bi₂Cl₉表面结构在光吸收能力上尤为特别且敏感;二维结构的Cs₃Bi₂Br₉光吸收能力会受厚度影响;零维结构的Cs₃Bi₂I₉非常稳定,且几乎不受表面特性和晶体厚度的影响。     

Bi2MoO6/BiVO4异质结的水热合成和可见光催化活性

采用一步水热法制备Bi₂MoO₆/BiVO₄复合光催化剂. 利用X 射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、高分辨透射电子显微镜(HRTEM)等手段对其晶体结构和微观结构进行了表征. 结果表明, Bi₂MoO₆纳米粒子沉积在BiVO₄纳米片表面从而形成异质结结构. 紫外-可见漫反射光谱(UV-Vis DRS)表明所制备的Bi₂MoO₆/BiVO₄异质结较纯相Bi₂MoO₆和BiVO₄对可见光吸收更强. 由于形成异质结结构及其光吸收性能使Bi₂MoO₆/BiVO₄ 光催化活性有较大提高. 可见光下(λ>420 nm)光催化降解罗丹明B (RhB)实验结果表明,Bi₂MoO₆/BiVO₄光催化活性较纯相Bi₂MoO₆和BiVO₄高. Bi₂MoO₆/BiVO₄样品光催化性能提高的原因是Bi₂MoO₆和BiVO₄形成异质结, 从而有效抑制光生电子-空穴对的复合, 增大了可见光吸收范围及比表面积.     

I-辅助构建具有优异吸附与光催化性能的类红细胞状Bi2WO6

通过简单的水热法,在I^-辅助的情况下,首次在不使用任何有机封端剂的情况下,获得了均匀的类红细胞状Bi₂WO₆。为了分析影响Bi₂WO₆形貌的前提条件,我们尝试改变I^-浓度、水热时间和温度,并提出可能的生长机理。I^-吸附在Bi₂WO₆纳米片的表面,以防止纳米片过度积聚并引导它们形成类红细胞的结构。独特的层状结构一方面增加了比表面积并提供了更多的反应位点,另一方面还提高了表面酸度并提高了吸附能力。     

Screw‐Dislocation‐Driven Bidirectional Spiral Growth of Bi2Se3 Nanoplates

Bi₂Se₃ attracts intensive attention as a typical thermoelectric material and a promising topological insulator material. However, previously reported Bi₂Se₃ nanostructures are limited to nanoribbons and smooth nanoplates. Herein, we report the synthesis of spiral Bi₂Se₃ nanoplates and their screw‐dislocation‐driven (SDD) bidirectional growth process. Typical products showed a bipyramid‐like shape with two sets of centrosymmetric helical fringes on the top and bottom faces. Other evidence for the unique structure and growth mode include herringbone contours, spiral arms, and hollow cores. Through the manipulation of kinetic factors, including the precursor concentration, the pH value, and the amount of reductant, we were able to tune the supersaturation in the regime of SDD to layer‐by‐layer growth. Nanoplates with preliminary dislocations were discovered in samples with an appropriate supersaturation value and employed for investigation of the SDD growth process.     

Effect of Screw-Dislocation on Electrical Properties of Spiral-Type Bi2Se3 Nanoplates

We systematically investigated the electrical properties of spiral-type and smooth Bi₂Se₃ nanoplates through field effect transistor and conductive atomic force microscopy (CAFM) measurement. It is observed that both nanoplates possess high conductivity and show metallic-like behavior. Compared to the smooth nanoplate, the spiral-type one exhibits the higher carrier concentration and lower mobility. CAFM characterization reveals that the conductance at the screw-dislocation edge is even higher than that on the terrace, implying that the dislocation can supply excess carriers to compensate the low mobility and achieve high conductivity. The unique structure and electrical properties make the spiral-type Bi₂Se₃ nanoplates a good candidate for catalysts and gas sensors.     

Controlled synthesis of topological insulator nanoplate arrays on mica

The orientation- and position-controlled synthesis of single-crystal topological insulator (Bi(2)Se(3) and Bi(2)Te(3)) nanoplate arrays on mica substrates was achieved using van der Waals epitaxy. Individual ultrathin nanoplates with the lateral dimension up to ~0.1 mm or uniform thickness down to 1-2 nm were produced. Single-Dirac-cone surface states of nanoplate aggregates were confirmed by angle-resolved photoemission spectroscopy measurements. The large-grain-size, single-crystal nanoplate arrays grown on mica can act as facile platforms for a combination of spectroscopy and in situ transport measurements, which may open up new avenues for studying exotic physical phenomena, surface chemical reactions, and modification in topological insulators.     

Unexpected Room‐Temperature Ferromagnetism in Nanostructured Bi2Te3

There is an urgent need for the development in the field of the magnetism of topological insulators, owing to the necessity for the realization of the quantum anomalous Hall effect. Herein, we discuss experimentally fabricated nanostructured hierarchical architectures of the topological insulator Bi₂Te₃ without the introduction of any exotic magnetic dopants, in which intriguing room‐temperature ferromagnetism was identified. First‐principles calculations demonstrated that the intrinsic point defect with respect to the antisite Te site is responsible for the creation of a magnetic moment. Such a mechanism, which is different from that of a vacancy defect, provides new insights into the origins of magnetism. Our findings may pave the way for developing future Bi₂Te₃‐based dissipationless spintronics and fault‐tolerant quantum computation.     

微波加热制备空心和锯齿形貌Bi_2Te_3晶体(英文)

Well-crystallized Bi₂Te₃ hollow spheres and nanosaws were prepared by microwave heating. Both the ionic liquid and the microwave heating play important role in the formation of the above nanostructures. Hollow spheres can not be obtained only by electronic stove heating, while the addition of ionic liquid leads to fast preparation of nanosaws structure under microwave heating conditions. The similar experimental results have been observed in the preparation of Bi₂S₃, Sb₂S₃ and Bi₂Se₃ nanostructures.     

Morphology Control of Bi2S3 Nanostructures and the Formation Mechanism

Bismuthinite (Bi₂S₃) nanostructures were prepared by a hydrothermal method with sodium ethylenediaminetetraacetate (EDTA‐Na₂). The morphology of Bi₂S₃ nanostructures was changed from a nanorod to a nanoplate by presence of the EDTA‐Na₂. The altered morphology was caused by the capping effect of EDTA‐Na₂ with Bi³⁺ ions, which induces the suboptimal growth direction due to partially blocking the preferential orientation direction. When the EDTA‐Na₂/Bi³⁺ molar ratio=1, the growth of Bi₂S₃ nanostructures was not allowed due to the chelating effect of EDTA‐Na₂. The obtained Bi₂S₃ nanorods, stacked nanorods, nanoplates and nanoparticles were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) pattern. A possible formation mechanism of these morphologies was proposed. The successful synthesis of various morphologies of nanostructured Bi₂S₃ may open up new possibilities for thermoelectric, electronic and optoelectronic uses of nanodevices based on Bi₂S₃ nanostructure.     

Intrinsically Low Thermal Conductivity and High Carrier Mobility in Dual Topological Quantum Material,n-Type BiTe

A challenge in thermoelectrics is to achieve intrinsically low thermal conductivity in crystalline solids while maintaining a high carrier mobility (μ). Topological quantum materials, such as the topological insulator (TI) or topological crystalline insulator (TCI) can exhibit high μ. Weak topological insulators (WTI) are of interest because of their layered hetero-structural nature which has a low lattice thermal conductivity (κ_lat). BiTe, a unique member of the (Bi₂)_m(Bi₂Te₃)_n homologous series (m:n=1:2), has both the quantum states, TCI and WTI, which is distinct from the conventional strong TI, Bi₂Te₃ (where m:n=0:1). Herein, we report intrinsically low κ_lat of 0.47–0.8 W m⁻¹ K⁻¹ in the 300–650 K range in BiTe resulting from low energy optical phonon branches which originate primarily from the localized vibrations of Bi bilayer. It has high μ≈516 cm² V⁻¹ s⁻¹ and 707 cm² V⁻¹ s⁻¹ along parallel and perpendicular to the spark plasma sintering (SPS) directions, respectively, at room temperature.     

Intrinsically Low Thermal Conductivity and High Carrier Mobility in Dual Topological Quantum Material,n‐Type BiTe

A challenge in thermoelectrics is to achieve intrinsically low thermal conductivity in crystalline solids while maintaining a high carrier mobility (μ). Topological quantum materials, such as the topological insulator (TI) or topological crystalline insulator (TCI) can exhibit high μ. Weak topological insulators (WTI) are of interest because of their layered hetero‐structural nature which has a low lattice thermal conductivity (κ_lat). BiTe, a unique member of the (Bi₂)_m(Bi₂Te₃)_n homologous series (m:n=1:2), has both the quantum states, TCI and WTI, which is distinct from the conventional strong TI, Bi₂Te₃ (where m:n=0:1). Herein, we report intrinsically low κ_lat of 0.47–0.8 W m^?1 K^?1 in the 300–650 K range in BiTe resulting from low energy optical phonon branches which originate primarily from the localized vibrations of Bi bilayer. It has high μ≈516 cm² V^?1 s^?1 and 707 cm² V^?1 s^?1 along parallel and perpendicular to the spark plasma sintering (SPS) directions, respectively, at room temperature.     

Synchrotron-radiation photoemission study of the V–VI layered compounds Bi2Te3, Bi2Se3, Sb2 Te3 and Sb2Te2Se

The valence band (VB) density of states and the binding energies of the weakly bound core levels have been measured by XUV photoelectron spectroscopy using synchrotron radiation for four V–VI layered compounds. Chemical shifts of the core levels are determined which support the partial ionicity of the bonds involved. The chemical shifts of the emission from two unequivalent crystal sites were shown to differ by less than 30 meV for the compounds Bi₂Te₃, Bi₂Se₃ and Sb₂Te₃.VB and core-level photoemission spectra for the V–VI compounds Bi₂Te₃, Bi₂Se₃, Sb₂Te₃ and Se₂Te₂Se have been presented. Chemical shifts of the Te 4d, Bi 5d, Sb 4d and Se 3d levels were determined, indicating partial ionicity of the mainly covalent bonds involved. Chemical-shift differences originating from atoms at two different crystal sites are <30 meV. In a simple model this implies that similar charge transfers do occur even though completely different bond orbitals were proposed for the and the AB⁽²⁾ bonds. Finally, the fact that no surface core-level shifts were observed tends to confirm the very weak influence of the van der Waals-like bonds on the B⁽²⁾ atoms.     

Highly Porous Thermoelectric Nanocomposites with Low Thermal Conductivity and High Figure of Merit from Large‐Scale Solution‐Synthesized Bi2Te2.5Se0.5 Hollow Nanostructures

To enhance the performance of thermoelectric materials and enable access to their widespread applications, it is beneficial yet challenging to synthesize hollow nanostructures in large quantities, with high porosity, low thermal conductivity (κ ) and excellent figure of merit (z T ). Herein we report a scalable (ca. 11.0 g per batch) and low‐temperature colloidal processing route for Bi₂Te_2.5Se_0.5 hollow nanostructures. They are sintered into porous, bulk nanocomposites (phi 10 mm×h 10 mm) with low κ (0.48 W m⁻¹ K⁻¹) and the highest z T (1.18) among state‐of‐the‐art Bi₂Te_3−x Se_x materilas. Additional benefits of the unprecedented low relative density (68–77 %) are the large demand reduction of raw materials and the improved portability. This method can be adopted to fabricate other porous phase‐transition and thermoelectric chalcogenide materials and will pave the way for the implementation of hollow nanostructures in other fields.