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Cuprate and iron-based superconductors are known as the only two types of high-Tc superconductors. The mechanism of high-Tc superconductivity is the most challenging issue in the field. Building accurate high-dimensional phase diagram and exploring key parameters that determine Tc, would be essential to the comprehension of high-Tc mechanism. The electronic phase diagrams of cuprate superconductors show complexity and diversity, for the strong coupling and interplay among lattice, orbital, charge and spin degrees of freedom. It is tough to construct a high-dimensional holographic phase diagram and obtain quantitative laws by traditional research methods. Fortunately, the high-throughput synthesis and fast screening techniques enable to probe the phase diagram via line-by-line or map scanning modes, and thereby are expected to obtain high-dimensional phase diagram and key superconducting parameters in a much efficient way. In this article, electronic phase diagrams of cuprate superconductors that are obtained mainly by electrical transport measurements, are briefly summarized in the view of cation substitutions, oxygen variation in the parent compounds, electric double-layer gating (electrostatic/electrochemical manipulation) and magnetic field. We introduce the preparation methods for combinatorial film based on the developed pulsed laser deposition and oxide molecular beam epitaxy techniques, as well as corresponding scale-span high-throughput measurement techniques. These high-throughput techniques have been successfully applied in the research of interface superconductivity, quantum phase transition, and so on. The novel high-throughput superconductivity research mode will play an indispensable role in the construction of the high-dimensional holographic phase diagram, the comprehension of high-Tc mechanism, and practical applications of superconductors. -
Keywords:
- high-Tc superconductor /
- cuprate superconductor /
- high-throughput combinatorial film /
- electronic phase diagram
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图 1 铜氧化物的晶体结构示意图, RE代表稀土元素原子 (a) “214”型空穴型铜氧化物的晶体结构; (b) “214”电子型铜氧化物的晶体结构; (c) YBa2Cu3O7超导体的晶体结构
Figure 1. An illustration of the crystal structure of cuprate superconductors, in which RE denotes rare earth atoms: (a) The crystal structure of hole-doped cuprates; (b) the crystal structure of electron-doped cuprates; (c) the crystal structure of YBa2Cu3O7.
图 2 空穴型铜氧化物La2–xSrxCuO4和电子型铜氧化物RE2–xCexCuO4的系统电子态相图. 其中SC, AFM, FM分别代表超导相、反铁磁序和铁磁序, 绿色虚线代表费米液体区域的边界. 在左半部分相图中, T*代表赝能隙打开的温度, 但其消失的位置仍有争议. 另外, 欠掺杂区域存在电荷和自旋的局域态, 图中未标出. 在右半部分相图中, 反铁磁序(两条蓝色线分别代表电输运中面内磁电阻各向异性出现的温度和upturn电阻出现的温度)消失于一个与费米面重构相关的量子临界点xFS, 超导相与铁磁序之间存在另一个量子临界点xc, 红色虚线代表奇异金属区域的边界
Figure 2. A systemic illustration of the phase diagram of hole- and electron-doped cuprates, in which SC, AFM, FM denote superconducting phase, antiferromagnetic order and ferromagnetic order, respectively, and green dashed line denotes the boundary of Fermi liquid regime. In the left part of the phase diagram, T* denotes the onset temperature of pseudogap, yet the disappearing temperature is still under debate. Charge and spin localized states exist in the underdoped region (not shown in this figure). In the right part of the phase diagram, antiferromagnetic order, diminishes in a quantum critical point xFS related to the reconstruction of Fermi surface, and the second quantum critical point xc is located at the edges of superconducting phase and ferromagnetic order. Two blue dashed lines associated with AF order are determined from anisotropic in-plane magnetoresistivity (higher) and the upturn of resistivity (lower), respectively. Red dashed line denotes the boundary of strange metal area.
图 4 通过退火和离子液体调控两种方法获得Pr2CuO4 ± δ薄膜的超导电性相图[64]. 蓝色区域是Tc与c轴晶格常数的依赖关系, 黄色区域(SC I和SC II)是Tc与门电压的依赖关系
Figure 4. Phase diagrams of Pr2CuO4 ± δ on the basis of annealing and gating processes[64]. Side view: the superconducting dome as a function of the c-axis lattice constant; Elevation view: the superconducting dome as a function of gate voltage (SC I and SC II represent two domes in positive and negative voltages, respectively).
图 7 基于分子束外延技术的组合薄膜生长技术示意图 (a) 蒸发源出来的分子束在空间的分布; (b) 石英振荡器所定标的沉积速率的空间分布
Figure 7. An illustration of combinatorial molecular beam epitaxy (COMBE): (a) The sketch of the distribution of atomic beam evaporated from the source; (b) the spatial distribution of the deposition rate calibrated by the quartz oscillator.
图 8 Fe-B二元成分组合薄膜的不同位置的电阻-温度依赖关系; (b) 64弹性探针阵列多通道电阻测量装置实物照片; (c) 左图中放大区域的交流磁化率测试结果[85]
Figure 8. (a) Mapping of the temperature dependence of resistivity on the Fe-B composition spread film; (b) a 64-pogo-pin-array probe; (c) diamagnetic signal measured by AC susceptibility on the same chip where resistive drop was observed[85].
图 10 LCCO组合薄膜的输运测试结果 (a) 第一次光刻采用的光刻图样; (b) 第一次光刻结束后各个桥路的R-T曲线, 超导转变温度随着掺杂的增加而逐渐降低, 到接近x = 0.19的一端超导电性消失; (c) 第二次光刻采用的光刻图样; (d) 第二次光刻结束后各个通道的R-T曲线; (e) 第三次光刻采用的光刻图样, 此时名义成分分辨率为0.0002; (f) 第三次光刻结束后各个桥路的R-T曲线
Figure 10. The results of electrical transport measurements for LCCO combinatorial film: (a) The pattern in the first step lithography; (b) the R-T curves of different channels in the first step lithography. The Tc decreases with increasing Ce doping; (c) the pattern in the second step lithography; (d) the R-T curves of different channels in the second step lithography; (e) the pattern in the third step lithography, where the nominal resolution of composition is 0.0002; (f) the R-T curves of different channels in the third step lithography.
图 11 (a) 组合激光分子束外延-扫描隧道显微镜联合系统; 内插: 旋转掩膜制备组合薄膜示意图; (b) 此设备生长出的梯度厚度FeSe薄膜R-T曲线; (c) 梯度厚度FeSe薄膜样品Tc0与厚度的依赖关系; (d) 该设备生长的FeSe薄膜原位原子分辨图
Figure 11. (a) The photograph of the combinatorial laser molecular beam epitaxy system integrated with low temperature scanning tunneling microscopy. Inset: Schematic diagram of the combinatorial film deposition stages; (b) temperature dependence of the resistance of the FeSe film with gradient thickness; (c) thickness dependence of Tc0 for a gradient thickness film; (d) atomic image of FeSe film fabricated in the system.
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