Superconductivity in Novel Actinide Filled Boron Carbon Clathrates
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摘要: Ac元素作为锕系第一号元素，AcH10的超导转变温度（Tc）达到251 K，是潜在的室温超导体。XB3C3（X表示不同的金属掺杂元素）是新发现的sp3笼型化合物，同时具有强共价特性和超导特性，是潜在的高温超导材料。采用第一性原理密度泛函理论，探索以XB3C3、XB2C4和XB4C2笼型结构为原型、引入Ac元素掺杂的AcB3C3、AcB2C4和AcB4C2的晶体结构、晶格动力学、电子性质和超导特性。研究发现：AcB2C4在0～200 GPa区间内难以合成；常压下AcB3C3表现为间接带隙半导体，带隙宽度约为1.154 eV。根据力学稳定性判据可知，AcB3C3和AcB4C2是弹性稳定的具有较高硬度和刚度的脆性材料。同时，常压下AcB4C2表现出超导特性，超导转变温度达到1.565 K。随着压强的增加，超导转变温度呈现先降低后升高的变化趋势，其超导机制由中频声子主导转变为低频与中频声子的共同作用。研究结果可为实验合成笼型化合物超导材料提供理论指导，为探索具有高超导转变温度的超导材料提供新思路。Abstract: Recently, a large number of theoretical and experimental studies have reported the emergence of a new sp3 clathrate XB3C3, where X represents different metal doping elements. The potential high-temperature superconducting materials have been discovered. New-typical cage material with both strong covalent and superconducting properties has important scientific research significance. In recent years, Ac discovered as the first element of the actinide series, AcH10 has a superconducting transition temperature (Tc) of 251 K, making it a potential room temperature superconductor. Therefore, in this article, first principles density functional theory is used to explore the crystal structure, lattice dynamics, electronic properties, and superconducting properties of AcB3C3, AcB2C4, and AcB4C2 doped with Ac elements based on the cage structures of XB3C3, XB2C4, and XB4C2. Research has found that AcB2C4 is difficult to synthesize within the 0–200 GPa range, and AcB3C3 exhibits an indirect bandgap semiconductor with a bandgap width of approximately 1.154 eV at atmospheric pressure. Based on the mechanical stability criterion, it can be inferred that AcB3C3 and AcB4C2 are brittle materials with high hardness and stiffness that are elastically stable. At the same time, AcB4C2 exhibits superconducting properties at ambient pressure, with Tc reaching 1.565 K. It has been observed that as pressure increases, the Tc value exhibits a trend of initially decreasing and then increasing. The superconducting mechanism is mainly influenced by intermediate-frequencies phonons, which then shift to the combination of low-frequencies and intermediate-frequencies phonons. This study provides guidance for the experimental synthesis of cage type compound superconducting materials and provides new ideas for exploring superconducting materials with high superconducting transition temperature.
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图 1 压强为 0 GPa时AcB3C3、AcB2C4和AcB4C2的晶体结构
Figure 1. Crystal structures of AcB3C3, AcB2C4, and AcB4C2 at 0 GPa
图 2 不同压力下AcBxCy（x=2, 3, 4；y=4, 3, 2）体系的分解焓(当p=0 GPa时，参考相为fcc-Ac单质相、α-B12单质相和六方石墨相；当p=100 GPa和p=200 GPa时，参考相为fcc-Ac单质相、α-Ga型B单质相和金刚石相)
Figure 2. Decomposition enthalpy diagrams of AcBxCy (x=2, 3, 4 and y=4, 3, 2) system at different pressures ( At 0 GPa, the reference phases are the fcc-Ac elemental phase, α-B12 elemental phase, and hexagonal graphite phase. At 100 and 200 GPa, the reference phases are the fcc-Ac elemental phase, α-Ga type B elemental phase, and diamond phase.)
图 3 AcB3C3和AcB4C2在0 GPa压强下的声子色散谱
Figure 3. Phonon dispersion spectra of AcB3C3 and AcB4C2 at 0 GPa
图 4 AcB3C3和AcB4C2在0 GPa下的原子轨道投影电子能带和分立电子态密度
Figure 4. Atomic orbital projected electron band and discrete electron density of state of AcB3C3 and AcB4C2 at 0 GPa
图 5 0 GPa时Ac-6d轨道、B-2p轨道和C-2p轨道在AcB4C2的费米面上的权重
Figure 5. Weights of Ac-6d orbitals, B-2p orbitals, and C-2p orbitals on the Fermi surfaces of AcB4C2 at 0 GPa
图 6 AcB3C3和AcB4C2在0 GPa下的三维局域电荷密度
Figure 6. Three-dimensional electron localization function of AcB3C3 and AcB4C2 at 0 GPa
图 7 (a) 不同压强下AcB4C2的声子频率对电声耦合参数λ的贡献， (b) p=0 GPa时AcB4C2的超导特性
Figure 7. (a) Contribution of phonon frequencies of AcB4C2 to electroacoustic coupling parameters λ at different pressures,(b) superconducting properties of AcB4C2 at 0 GPa
表 1 常压下AcB3C3和AcB4C2的物性参数
Table 1. Physical parameters of AcB3C3 and AcB4C2 at ambient pressure
System C11/GPa C12/GPa C13/GPa C16/GPa C33/GPa C44/GPa $Pm \overline{3} n $-AcB3C3 859.97 185.78 327.12 I4/mmm-AcB4C2 715.43 241.16 114.38 0 814.58 274.96 System C66/GPa B/GPa G/GPa E/GPa ν B/G $Pm \overline{3} n $-AcB3C3 410.51 331.11 782.85 0.18 1.24 I4/mmm-AcB4C2 303.83 353.92 289.12 681.72 0.18 1.22 
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表 2 不同压强下AcB4C2的物性参数
Table 2. Physical parameters of of AcB4C2 at different pressures
Space group p/GPa 〈ωlog〉/K λ Tc/K N(EF)/
[states/(spin·Ry·Unit)]μ*=0.10 μ*=0.13 I4/mmm 0 747.309 0.358 1.565 0.520 6.153 50 862.377 0.307 0.515 0.094 5.804 100 895.107 0.302 0.455 0.076 5.872 150 896.673 0.316 0.700 0.147 6.206 200 883.648 0.341 1.304 0.372 6.557
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