浅析电子型掺杂铜氧化物超导体的退火过程

铜氧化物高温超导体的发现, 打破了基于电声子相互作用BCS理论所预言的超导转变温度极限, 掀开了高温超导材料探索和高温超导机理研究的序幕. 根据掺杂类型的不同, 铜氧化物超导材料可以分为空穴型掺杂和电子型掺杂两类. 受限于样品, 对电子型掺杂铜氧化物的研究工作远少于空穴型掺杂体系. 本文简要回顾有关电子型掺杂铜氧化物超导体近期研究成果, 通过对比电子型掺杂和空穴型掺杂铜氧化物的相图来阐明电子型掺杂铜氧化物的研究对探索高温超导机理的必要性, 并特别针对电子型掺杂样品制备中的关键因素“退火过程”展开讨论. 结合课题组最新实验结果和相关实验报道我们发现电子型掺杂铜氧化物超导体在制备过程中除受到温度和氧分压的影响外, 退火效果还受到界面应力的强烈调制. 在综合考虑样品生长过程中温度、气氛及应力等多种因素的基础上, 探讨了“保护退火”方法导致电子型体系化学掺杂相图变化的起因.     

Electronic Phase Separation in Iron Selenide(Li,Fe)OHFeSe Superconductor System

The phenomenon of phase separation into antiferromagnetic(AFM) and superconducting(SC) or normal-state regions has great implication for the origin of high-temperature(high-T_c) superconductivity. However, the occurrence of an intrinsic antiferromagnetism above the T_c of(Li,Fe)OHFe Se superconductor is questioned. Here we report a systematic study on a series of(Li,Fe)OHFe Se single crystal samples with T_c up to ～41 K. We observe an evident drop in the static magnetization at T_(afm) ～ 125 K, in some of the SC(T_c 38 K, cell parameter c■9.27 ?) and non-SC samples. We verify that this AFM signal is intrinsic to(Li,Fe)OHFe Se. Thus, our observations indicate mesoscopic-to-macroscopic coexistence of an AFM state with the normal(below T_(afm)) or SC(below T_c) state in(Li,Fe)OHFe Se. We explain such coexistence by electronic phase separation, similar to that in high-T_c cuprates and iron arsenides. However, such an AFM signal can be absent in some other samples of(Li,Fe)OHFe Se, particularly it is never observed in the SC samples of T_c 38 K, owing to a spatial scale of the phase separation too small for the macroscopic magnetic probe. For this case, we propose a microscopic electronic phase separation. The occurrence of two-dimensional AFM spin fluctuations below nearly the same temperature as T_(afm), reported previously for a(Li,Fe)OHFe Se(T_c ～ 42 K) single crystal, suggests that the microscopic static phase separation reaches vanishing point in high T_c(Li,Fe)OHFe Se. A complete phase diagram is thus established. Our study provides key information of the underlying physics for high-T_c superconductivity.     

面向宽温域功能器件的连续组分外延铁电薄膜

Ba_xSr(1–x)TiO₃ (BST)铁电薄膜因为拥有高介电常数、强电场调谐性和较低的微波频段介电损耗可应用于微波可调谐器件.然而铁电材料中普遍存在的介电常数-温度依赖性使得常规单组分铁电薄膜的高可调率温区受制于相变温度,难以满足宽温域适用性的需求.为研究可用于宽温域功能器件的铁电薄膜,采用脉冲激光沉积(PLD)技术制备了单组分Ba_0.5Sr_0.5TiO₃薄膜、Ba_0.2Sr_0.8TiO₃薄膜以及Ba_0.2Sr_0.8TiO₃/Ba_0.5Sr_0.5TiO₃异质结构薄膜.通过对比其介电性能,发现垂直方向上Ba/Sr组分分布可有效改善BST薄膜的温度依赖性,然而异质结构的构建可能带来界面问题,同时也使其品质因子难以提升.本文提出采用独特的水平方向连续组分薄膜制备技术制备BST组合薄膜,有...     

电子型高温超导体/铁电体/巨磁阻材料异质结的生长及其电输运性质的研究

本文中采用脉冲激光沉积的方法原位制备了结构完整的La1.89Ce0.11CuO4(LCCO)/Ba0.7Sr0.3TiO3(BST)/La0.67Sr0.33MnO3(LSMO)三层膜,并在此基础上制得了类似P-I-N型的全钙钛矿结构材料异质结.在不同的温度区间对其电输运性质进行了测量.测量结果表明随着充当绝缘层的Ba0.7Sr0.3TiO3的厚度的变化,异质结的电输运机制也在变化.当其厚度到达25纳米时,整个结在低温区呈现良好的整流特性.     

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.     

Effect of Mn substitution on superconductivity in iron selenide(Li,Fe)OHFeSe single crystals

We synthesize a series of Mn substituted(Li, Fe)OHFeSe superconductor single crystals via a modified ion-exchange method, with the Mn concentration z(the atomic ratio of Mn:Se) ranging from 0 to 0.07. The distribution homogeneity of the Mn element incorporated into the lattice of(Li, Fe)OHFeSe is checked by combined measurements of high-angleannular-dark-field(HAADF) imaging and electron energy-loss spectroscopy(EELS). Interestingly, we find that the superconducting transition temperature T_c and unit cell parameter c of the Mn-doped(Li, Fe)OHFeSe samples display similar V-shaped evolutions with the increasing dopant concentration z. We propose that, with increasing doping level, the Mn dopant first occupies the tetrahedral sites in the(Li, Fe)OH layers before starting to substitute the Fe element in the superconducting Fe Se layers, which accounts for the V-shaped change in cell parameter c. The observed positive correlation between the T_c and lattice parameter c, regardless of the Mn doping level z, indicates that a larger interlayer separation, or a weaker interlayer coupling, is essential for the high-T_c superconductivity in(Li, Fe)OHFeSe. This agrees with our previous observations on powder, single crystal, and film samples of(Li, Fe)OHFeSe superconductors.     

脉冲激光沉积技术制备超导薄膜的研究进展

超导薄膜不仅在超导应用方面扮演着举足轻重的角色，而且是超导机理研究的良好载体，是连接超导应用和机理的桥梁。脉冲激光沉积(PLD)是最常用的超导薄膜制备技术之一。本文综述了PLD技术制备铜氧化物、铁基、氮化物、钛氧化物等超导薄膜的研究进展，并介绍了与高温超导薄膜应用相关的两种PLD新技术：超导带材和大面积薄膜制备。最后，本文介绍了基于材料基因工程的高通量组合薄膜技术在高温超导研究上的典型成功案例。继续发展和使用该实验技术，构建与高温超导相关的高维相图和定量规律，有望实现机理研究实验上从量变到质变的全面突破。     

Bi1-xLaxFeO3±δ薄膜的快速制备及铁电性

样品的制备是对影响样品质量的各个工艺参数进行优化的过程. 传统的试错法是对各个参数逐个进行尝试, 需要的周期较长. 与传统的单参数尝试法相比, 高通量样品制备方法可以对参数实现并行筛选, 因而极大地缩短了优化工艺所需的时间. 本工作借助高通量制备方法成功实现系列镧掺杂BiFeO₃薄膜的快速优化, 包括对烧结温度、镧元素含量和高温固态反应气氛等关键工艺参数的快速筛选, 同时分析了不同生长条件下样品的结构并测试了其铁电性. 实验结果表明: 1) 560 ℃ 烧结可得到单相薄膜; 2)测量不同La含量样品的铁电性, 发现当E=75 kV/cm时, La=15%的样品剩余极化值(2Pr)最大, 约为26.7 μC/cm²; 3) 在纯氧气氛下烧结有助于得到结晶性更好的单相Bi_0.75La_0.25FeO_3±δ 薄膜, 并且能够提高薄膜的铁电性.     

Distinction between critical current effects and intrinsic anomalies in the point-contact Andreev reflection spectra of unconventional superconductors

In this work,we discuss the origin of several anomalies present in the point-contact Andreev reflection spectra of(Li_(1-x)Fe_x)OHFeSe,LiTi_2O_4,and La_(2-x)Ce_xCuO_4.While these features are similar to those stemming from intrinsic superconducting properties,such as Andreev reflection,electron-boson coupling,multigap superconductivity,d-wave and p-wave pairing symmetry,they cannot be accounted for by the modified Blonder–Tinkham–Klapwijk(BTK) model,but require to consider critical current effects arising from the junction geometry.Our results point to the importance of tracking the evolution of the dips and peaks in the differential conductance as a function of the bias voltage,in order to correctly deduce the properties of the superconducting state.     

电子型高温超导体／铁电体／巨磁阻材料异质结的生长及其电输运性质的研究

本文中采用脉冲激光沉积的方法原位制备了结构完整的La1.89Ce0.11CuO4（LCCO）／Ba0．7Sr0.33TiO3（BST）／La0.67Sr0．33MnO3（LSMO）三层膜，并在此基础上制得了类似P-I-N型的全钙钛矿结构材料异质结．在不同的温度区间对其电输运性质进行了测量．测量结果表明随着充当绝缘层的Ba0．7Sr0．3TiO3的厚度的变化，异质结的电输运机制也在变化．当其厚度到达25纳米时，整个结在低温区呈现良好的整流特性．