Doping effects of transition metals on the superconductivity of (Li,Fe)OHFeSe films

The doping effects of transition metals(TMs = Mn, Co, Ni, and Cu) on the superconducting critical parameters are investigated in the films of iron selenide(Li,Fe)OHFe Se. The samples are grown via a matrix-assisted hydrothermal epitaxy method. Among the TMs, the elements of Mn and Co adjacent to Fe are observed to be incorporated into the crystal lattice more easily. It is suggested that the doped TMs mainly occupy the iron sites of the intercalated(Li,Fe)OH layers rather than those of the superconducting Fe Se layers. We find that the critical current density J_c can be enhanced much more strongly by the Mn dopant than the other TMs, while the critical temperature T_c is weakly affected by the TM doping.     

Revisiting the Electron-Doped SmFeAsO:Enhanced Superconductivity up to58.6K by Th and F Codoping

In the iron-based high-T_c bulk superconductors, T_c above 50 K was only observed in the electron-doped 1111-type compounds. Here we revisit the electron-doped SmFeAsO polycrystals to make a further investigation for the highest T_c in these materials. To introduce more electron carriers and less crystal lattice distortions, we study the Th and F codoping effects into the Sm-O layers with heavy electron doping. Dozens of Sm_(1-x)Th_x FeAsO_(1-y)F_y samples are synthesized through the solid state reaction method, and these samples are carefully characterized by the structural, resistive, and magnetic measurements. We find that the codoping of Th and F clearly enhances the superconducting T_c more than the Th or F single-doped samples, with the highest record T_c up to 58.6 K when x=0.2 and y=0.225. Further element doping causes more impurities and lattice distortions in the samples with a weakened superconductivity.     

Superconductivity in Sm-doped CaFe_2As_2 single crystals

In this article,the Sm-doping single crystals Ca_(1-x)Sm_xFe_2As_2(x = 0 ~0.2) were prepared by the Ca As flux method,and followed by a rapid quenching treatment after the high temperature growth.The samples were characterized by structural,resistive,and magnetic measurements.The successful Sm-substitution was revealed by the reduction of the lattice parameter c,due to the smaller ionic radius of Sm~(3+)than Ca~(2+).Superconductivity was observed in all samples with onset T_c varying from 27 K to 44 K upon Sm-doping.The coexistence of a collapsed phase transition and the superconducting transition was found for the lower Sm-doping samples.Zero resistivity and substantial superconducting volume fraction only happen in higher Sm-doping crystals with the nominal x 0.10.The doping dependences of the c-axis length and onset T_c were summarized.The high-T_c observed in these quenched crystals may be attributed to simultaneous tuning of electron carriers doping and strain effect caused by lattice reduction of Sm-substitution.     

FeSe基超导单晶与薄膜研究新进展:自旋向列序、电子相分离及高临界参数

FeSe基超导体的超导临界温度可大范围调控,物理现象丰富,是非常规超导机理研究的热点.由于较高的超导临界参数及易于加工等特点,FeSe基超导体在超导应用开发方面也日益受到重视.大尺寸高质量的单晶和薄膜形态的FeSe基超导材料,对于相关基础科学研究和应用开发都极为重要.作者近年来先后开发和发明了水热离子交换（ion-exchange）、离子脱插（ion-deintercalation）、基底辅助水热外延生长方法,成功解决了二元FeSe和插层（Li,Fe）OHFeSe超导体高质量单晶和薄膜的生长和物性调控难题.进而在相关物理问题的研究中取得新进展,包括发现二元FeSe中自旋向列序与超导电性密切相关,观测到（Li,Fe）OHFeSe中的电子相分离现象.此外,（Li,Fe）OHFeSe超导薄膜呈现很高的超导临界电流密度和上临界磁场,其应用前景值得关注.     

Superconductivity at 44.4 K achieved by intercalating EMIM~+ into FeSe

Superconductivity with transition temperature Tc above 40 K was observed in protonated Fe Se(Hy-Fe Se) previously with the ionic liquid EMIM-BF4 used in the electrochemical process. However, the real superconducting phase is not clear until now. And detailed structural, magnetization, and electrical transport measurements are lacking. By using similar protonating technique on Fe Se single crystals, we obtain superconducting samples with Tc above 40 K. We show that the obtained superconducting phase is not Hy-Fe Se but actually an organic-ion(C_6H_(11)N_2~+ referred to as EMIM~+)-intercalated phase(EMIM)x Fe Se. By using x-ray diffraction technique, two sets of index peaks corresponding to different c-axis lattice constants are detected in the obtained samples, which belong to the newly formed phase of intercalated(EMIM)_x Fe Se and the residual Fe Se, respectively. The superconductivity of(EMIM)x Fe Se with Tc of 44.4 K is confirmed by resistivity and magnetic susceptibility measurements. Temperature dependence of resistivity with different applied magnetic fields reveals that the upper critical field H_(c2) is quite high, while the irreversibility field Hirris suppressed quickly with increasing temperature till about 20 K. This indicates that the resultant compound has a high anisotropy with a large spacing between the Fe Se layers.     

铁硒基超导研究新进展:高质量(Li,Fe)OHFeSe单晶薄膜

单晶薄膜形态的高温超导材料对于相关基础科学研究和应用开发都极为重要.多带的铁基高温超导体往往呈现丰富的物理现象,并具有较高的超导临界参数.特别是近年发现的插层（Li,Fe）OHFeSe超导体,无论对高温超导机理还是应用研究而言,都日益受到重视,已成为铁基家族中重要的典型材料.但是,该化合物含有OH键,加热易分解.因此,现有的常规高温成膜技术均不适用于生长该薄膜材料.为解决这一生长难题,我们最近发明了基体辅助水热外延生长法,实现了超导薄膜制备技术上的突破.本文简要介绍用此软化学成膜技术首次成功制备出（Li,Fe）OHFeSe单晶薄膜.该薄膜材料具有优良的结晶质量和较高的超导临界参数,特别是其高的临界电流密度和上临界场对应用开发有实际价值.因此,（Li,Fe）OHFeSe超导单晶薄膜的成功合成,为机理研究和应用开发分别提供了重要的实验载体和备选材料.另外,该薄膜技术也有望应用于其他功能材料的探索与合成,尤其是对常规手段难以获取的材料更具重大价值.     

Superconductivity in Li OHFe S single crystals with a shrunk c-axis lattice constant

By using a hydrothermal ion-exchange method, we have successfully grown superconducting crystals of Li OHFe S with Tcof about 2.8 K. Being different from the sister sample(Li1-xFex)OHFe Se, the energy dispersion spectrum analysis on Li OHFe S shows that the Fe/S ratio is very close to 1:1, suggesting an almost charge neutrality and less electron doping in the Fe S planes of the system. Comparing with the non superconducting Li OHFe S crystal, each peak of the X-ray diffraction pattern of the superconducting crystal splits into two, and the diffraction peaks locating at lower reflection angles are consistent with that of non-superconducting ones. The rest set of diffraction peaks with higher reflection angles is corresponding to the superconducting phase, suggesting that the superconducting phase may has a shrunk c-axis lattice constant. Magnetization measurements indicate that the magnetic shielding due to superconductivity can be quite high under a weak magnetic field. The resistivity measurements under various magnetic fields show that the upper critical field is quite low, which is similar to the tetragonal Fe S superconductor.     

Phase diagram of K(x)Fe(2-y)Se(2-z)S(z) and the suppression of its superconducting state by an Fe2-Se/S tetrahedron distortion

We report structurally tuned superconductivity in a K(x)Fe(2-y)Se(2-z)S(z) (0 ≤ z ≤ 2) phase diagram. Superconducting T(c) is suppressed as S is incorporated into the lattice, eventually vanishing at 80% of S. The magnetic and conductivity properties can be related to stoichiometry on a poorly occupied Fe1 site and the local environment of a nearly fully occupied Fe2 site. The decreasing T(c) coincides with the increasing Fe1 occupancy and the overall increase in Fe stoichiometry from z = 0 to z = 2. Our results indicate that the irregularity of the Fe2-Se/S tetrahedron is an important controlling parameter that can be used to tune the ground state in the new superconductor family.     

The superconducting transition temperatures of Fe(1+x)Se(1-y), Fe(1+x)Se(1-y)Te(y) and (K/Rb/Cs)(z)Fe(2-x)Se2

In a recent contribution to this journal, it was shown that the transition temperatures of optimal high-T(C) compounds obey the algebraic relation T(C0) = k(-1)(B)/?ζ, where ? is related to the mean spacing between interacting charges in the layers, ζ is the distance between interacting electronic layers, β is a universal constant and k(B) is Boltzmann's constant. The equation was derived assuming pairing based on interlayer Coulomb interactions between physically separated charges. This theory was initially validated for 31 compounds from five different high-T(C) families (within an accuracy of ±1.37 K). Herein we report the addition of Fe(1+x)Se(1-y) and Fe(1+x)Se(1-y)Te(y) (both optimized under pressure) and A(z)Fe(2-x)Se(2) (for A = K, Rb or Cs) to the growing list of Coulomb-mediated superconducting compounds in which T(C0) is determined by the above equation. Doping in these materials is accomplished through the introduction of excess Fe and/or Se deficiency, or a combination of alkali metal and Fe vacancies. Consequently, a very small number of vacancies or interstitials can induce a superconducting state with a substantial transition temperature. The confirmation of the above equation for these Se-based Fe chalcogenides increases to six the number of superconducting families for which the transition temperature can be accurately predicted.     

Synthesis of a new alkali metal-organic solvent intercalated iron selenide superconductor with T(c)?≈?45?K

We report on a new iron selenide superconductor with a T(c) onset of 45?K and the nominal composition Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2), synthesized via intercalation of dissolved alkaline metal in anhydrous pyridine at room temperature. This superconductor exhibits a broad transition, reaching zero resistance at 10?K. Magnetization measurements reveal a superconducting shielding fraction of approximately 30%. Analogous phases intercalated with Na, K and Rb were also synthesized and characterized. The superconducting transition temperature of Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2) is clearly enhanced in comparison to those of the known superconductors FeSe(0.98) (T(c)?～?8?K) and A(x)Fe(2-y)Se(2) (T(c)?～?27-32?K) and is in close agreement with critical temperatures recently reported for Li(x)(NH(3))(y)Fe(2-z)Se(2). Post-annealing of intercalated material (Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2)) at elevated temperatures drastically enlarges the c-parameter of the unit cell (～44%) and increases the superconducting shielding fraction to nearly 100%. Our findings indicate a new synthesis route leading to possibly even higher critical temperatures for materials in this class: by intercalation of organic compounds between Fe-Se layers.     

硼掺杂拓扑绝缘体Bi2Se3单晶的电输运性质研究

本文首次报道了用自助溶剂法(self-flux)制备优良的硼(B)掺杂硒化铋(Bi2BxSe3-x)样品的探索。实验结果显示掺杂样品中大部分B是以替代Se位方式存在,少量B以插入Bi2Se3晶格或范德瓦尔斯间隙的形式存在。当B的含量逐渐增加时,Bi2Se3的晶格常数c先减小后增加,且样品具有清晰的层状结构。掺杂量x=0.05的样品局部区域出现纳米带结构,同时该样品在低温下出现了明显的金属-绝缘转变现象。Bi2Se3样品电阻率随掺杂含量的增加而增加,表明B掺杂提高了样品表面态对整体电导的贡献,同时纳米带结构也有助于增加表面态的贡献。     

Doping Mn into(Li_(1-x)Fe_x)OHFe_(1-y)Se superconducting crystals via ion-exchange and ion-release/introduction syntheses

We report the success in introducing Mn into(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconducting crystals by applying two different hydrothermal routes, ion e_xchange(1-step) and ion release/introduction(2-step). The micro-region _x-ray diffraction and energy dispersive _x-ray spectroscopy analyses indicate that Mn has been doped into the lattice, and its content in the 1-step fabricated sample is higher than that in the 2-step one. Magnetic susceptibility and electric transport properties reveal that Mn doping influences little on the superconducting transition, regardless of 1-step or 2-step routes. By contrast, the characteristic temperature T*, at which the negative Hall coefficient reaches its minimum, is significantly reduced by Mn doping.This implies that the hole carriers contribution is obviously modified, and hence the hole band might have no direct relationship with the superconductivity in(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconductors. Our present hydrothermal methods of ion e_xchange and ion release/introduction provide an efficient way for elements substitution/doping into(Li_(1-_x)Fe_x)OHFe_(1-y) Se superconductors, which will promote the in-depth investigations on the role of multiple electron and hole bands and their interplay with the high-temperature superconductivity in the FeSe-based superconductors.     

纳米Ce1-x(Fe0.5La0.5)xO2-δ固溶体的水热合成及光谱分析

采用水热方法合成Ce1-x(Fe0.5 La0.5)xO2-δ固溶体.利用X射线衍射技术(X-ray diffraction technique,XRD)表征样品的相结构,并对固溶体的晶胞参数进行拟合,通过紫外可见漫反射光谱(UV-Vis diffraction spectrum)及拉曼光谱(Raman spectru...     

Potassium doping effect on the lattice softening and electronic structure of Ba(1-x)K(x)Fe(2)As(2) probed by X-ray absorption spectroscopy

Ba(1-x)K(x)Fe(2)As(2) superconducting samples (x = 0, 0.2, 0.4, 0.5) were synthesized by the solid-state reaction method. In this contribution the doping effect of potassium on the lattice dynamics in this newly discovered Ba(1-x)K(x)Fe(2)As(2) superconductor has been investigated by extended X-ray absorption fine-structure spectroscopy. The analysis shows that with potassium doping an increased disorder in the iron layers is mainly related to the softening of the Fe-Fe bond. Information about the electronic structure of these materials has also been obtained by looking at the X-ray absorption near-edge structure spectra that point out the presence of holes in the Fe-3d/As-4p hybridized orbital of the BaFe(2)As(2)-based system.     

Revised superconducting phase diagram of hole-doped Na(x)(H3O)(z)CoO2 x yH(2)O

We have studied the superconducting phase diagram of NaxCoO2.yH(2)O as a function of electronic doping, characterizing our samples both in terms of Na content x and the Co valence state. Our findings are consistent with a recent report that intercalation of H3O+ ions into NaxCoO2, together with water, acts as an additional dopant, indicating that Na substoichiometry alone does not control the electronic doping of these materials. We find a superconducting phase diagram where optimal T(C) is achieved through a Co valence range of 3.24-3.35, while T(C) decreases for materials with a higher Co valence. The critical role of dimensionality in achieving superconductivity is highlighted by similarly doped nonsuperconducting anhydrous samples, differing from the superconducting hydrate only in interlayer spacing.     

Doping-induced change in the interlayer transport mechanism of Bi_{2}Sr_{2}CaCu_{2}O_{8+delta} near the superconducting transition temperature

We perform a detailed study of temperature, bias, and doping dependence of interlayer transport in the layered high temperature superconductor Bi_{2}Sr_{2}CaCu_{2}O_{8+delta}. We observe that the shape of interlayer characteristics in underdoped crystals exhibits a remarkable crossover at the superconducting transition temperature: from thermal activation-type above T_{c} to almost T-independent quantum tunneling-type below T_{c}. Our data provide insight into the nature of interlayer transport and indicate that its mechanism changes with doping: from the conventional single quasiparticle tunneling in overdoped to a progressively increasing Cooper pair contribution in underdoped crystals.     

First Principles Study on FeAs Single Layers

在广义梯度近似(GGA)和GGA+U的框架下,用第一性原理方法研究了用FeAs单层的简单模型来研究LaFeAsO和BaFe2As2的合理性. 对未掺杂的FeAs单层,优化的几何结构及其对应的电子结构与本体的性质差异较大,并且在单层中没有发现体相中的共线反铁磁基态. 另外,在单层中,As与Fe层之间在z方向的间距随电子和空穴掺杂浓度的变化也与实验结果不符,这些结果表明,在LaFeAsO和BaFe2As2中,FeAs层与其他层之间的相互作用是不可忽略的,用简单的FeAs单层来处理Fe基超导体需要考虑更多的修正     

Doping investigations of the spin-Peierls-system CuGeO3

We investigated the effect of doping CuGeO₃ with Zn, Ni, Mn and Mg on the Cu-site, and Al, Si, Ga, As, In, Sn, Sb and Ti on the Ge-site. The lattice parameters show a linear dependence on doping. The spin-Peierls (SP) transition temperature T_SP decreases linearly with increasing substitution, the slope depending on the dopant. For increasing Zn-content, a Néel-like groundstate which exhibits spin-flop-behaviour appears after the disappearence of the SP-ground-state. Si-and Ti-doped samples exhibit a similar phase in co-existence with the SP-groundstate.     

Influence of Mn doping on structural and optical properties of ZnO nano thin films synthesized by sol–gel technique

Undoped and Mn-doped ZnO samples with different percentages of Mn content (1, 5 and 10?at%) were synthesized by a dip-coating sol?Cgel method. We have studied the structural, chemical and optical properties of the samples by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible spectroscopy. The XRD spectra show that all the samples are hexagonal wurtzite structures. We note that doping favors c-axis orientation along (002) planes. Up to 5?at% of Mn doping level, the c-axis lattice parameter shifts towards higher values with the increase of manganese content in the films. The expansion of the lattice constant of ZnO?CMn indicates that Mn is really doped into the ZnO. The SEM investigations of all samples revealed that the crystallites are of nanometer size. The surface quality of the ZnO?CMn film increases with Mn doping but no significant change of the grain size is observed from SEM images. The transmittance spectra show that the transparency of all the samples is greater than 85?%. We note, also, that a small doping (1?%) lowered the refractive index while the thickness of the layers and the gap increase. However, on raising the proportion of Mn beyond 5?%, practically the same values of index and gap as pure ZnO are found.     

电子型FeSe基高温超导体的磁通束缚态与Majorana零能模

作为凝聚态物理中一类新奇准粒子态,Majorana零能模(Majorana zero mode)由于可用来实现拓扑量子计算而成为当前的研究热点.理论预言,Majorana零能模可作为特殊的束缚态出现在一些拓扑超导体的磁通涡旋中.但实际超导体磁通中还可能存在其他低能束缚态或杂质态,这给Majorana零能模的辨别和具体应用带来了困难.目前实验上寻找合适的拓扑超导体系、分辨出清晰的Majorana零能模仍然是十分迫切的.本文主要介绍最近利用高能量分辨的扫描隧道显微镜,对电子掺杂铁硒类超导体(Li,Fe)OHFeSe和单层FeSe/SrTiO3磁通态进行的研究.实验上在前者的自由磁通中观测到清晰的零能模,并进一步测量到Majorana零能模的重要特征—量子化电导.而在后者磁通中只发现常规Caroli-de Gennes-Matricon(CdGM)束缚态,反映出s波对称性的特征.这系列实验既为Majorana零能模物性的进一步研究提供了合适平台,也为澄清铁基超导体中拓扑超导电性的来源提供了线索.