镥团簇、内嵌过渡金属硅插合物和铕内嵌富勒烯膜的结构与性能预测
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摘要
由于具有纳米尺度的团簇，碳富勒烯，以及自旋电子学材料具有独特的几何结构，新颖的电子结构和磁特性，自从被发现以来便得到了人们的广泛关注。它们在小型电子器件的研制等方面是最有潜力的材料。近年来，随着密度泛函理论的不断改进和完善以及计算机性能的高速发展，基于密度泛函理论的第一性原理计算被广泛的应用于新材料的预测和研发。在本论文中，利用密度泛函理论计算对Lu_n(n=2-20)团簇，3d过渡金属掺杂第一类Si插合物MSi_(46)(M=Mn，Fe，Co，Ni)以及Ag(111)面Eu@C_(60)单分子层吸附的几何结构,电子结构以及磁性进行了系统的研究。研究结果如下：
(1)对于Lu_n(n=2-20)团簇，原子数小于16时Lu_n(n＜16)，它们的生长模式都是基于八面体的结构；当原子数大于16时，Lu_n(16≤n≤20)团簇出现了一个新的基于十面体的生长模式。Lu_4，Lu_8，Lu_(13)和Lu_(18)团簇具有较高的稳定性，它们的结合能比相应的相邻原子数Lu团簇的结合能要低。Lu_n(n=2-20)团簇的磁矩较小，都不超过4.00μB。当原子数n=2-8时，Lu_n团簇的磁矩交替增大，随原子数的增大，当n=9-20时，Lu_n团簇的磁矩出现了在0.00μB和1.00μB之间的奇偶交替现象。在原子数n=5处，Lu团簇的磁序发生转变，从铁磁性转变为亚铁磁性。这些结果为研究过渡金属从团簇转变到大块固体的结构演化，以及过渡金属团簇的磁性和电子结构提供了理论依据。
(2)在第一类Si插合物的硅二十笼子或者硅二十四笼子中心掺入单个3d过渡金属原子M(M=Mn，Fe，Co和Ni)后，硅插合物在电子结构和磁性上都出现了明显的变化。与未掺杂的Si_(46)插合物单胞相比，掺杂后MSiα46和MSiβ46的晶格常数均变小。当在硅二十笼子中心掺入Mn或者Co，以及在硅二十四笼子中心掺入Mn，Fe或者Ni原子后，形成的新的插合化合物都表现出half-metallic性质，并且均具有较大的磁矩。Mn，Fe，Co和Ni掺杂后，自旋磁矩分别为5.00μB，4.00μB，3.00μB和2.00μB。而当在硅二十笼子中心掺入Fe或者Ni，以及在硅二十四笼子中心掺入Co原子后，形成的新的插合化合物都表现出了semi-metallic性质，且具有较大的磁矩。Fe，Co和Ni掺杂后分别具有4.00μB，3.00μB和2.00μB的自旋磁矩。以上结果表明，MnSi_(46)是一个较好的半金属材料，将来可能被用于自旋电子学材料。
(3)当Eu@C_(60)单分子层吸附在Ag(111)面上时，我们发现Eu@C_(60)单分子层引起了Ag(111)表面的重构，Eu@C_(60)和Ag(111)之间的垂直距离要比C_(60)和Ag(111)之间的垂直距离要小0.05。在Ag(111)面上Eu@C_(60)单分子层的几何结构和C_(60)单分子层吸附在Ag(111)面上的几何结构相一致。其稳定结构为Eu@C_(60)的一个六边形的面朝向基底，而和这个六边形面相对的另外一个六边形面平行于基底。Eu@C_(60)/Ag(111)单胞具有较大的自旋磁矩，其大小为6.80μB，通过密立根电荷分析我们知道这个较大磁矩主要来源于Eu原子。Eu@C_(60)和Ag(111)之间没有形成较强的化学键，只有0.55e大小的电荷从Ag(111)中转移到了Eu@C_(60)之上。我们的研究结果为C_(60)富勒烯内包物的应用提供了理论依据。
Clusters with nano-scale, fullerenes and spintronics materials have attracted considerableinteresting, for there special geometry structure, novel electronic structure and magnetismproperties. They are promising materials for applications in small spintronics materials. Withthe improvement of density functional theory and the performanc of computer, the firstprinciples calculations based on density functional theory have been applied to the study ofnew materials. In this paper, using density functional theory, we have calculated the structure,electronic and magnetism properties of Lu_n(n=2-20) cluster,3d transition metal-doped type ISi clathrates MSi_(46)(M=Mn，Fe，Co，Ni) and Eu@C_(60)monolayer adsorbed on the surface ofAg(111). The results are as follows:
(1) For Lu_n(n=2-20) cluster, when the number of atoms are smaller than16, the growthpattern of Lu_n(n＜16) cluster are based on octahedral; when the number of atoms are morethan16, the Lu_n(16≤n≤20) cluster have a new growth pattern that based on decahedral. TheLu_4，Lu_8，Lu_(13)and Lu_(18)clusters have higher stability, their binding energise are lower thenthat of their neighbors. All the Lu_n(n=2-20) clusters has small spin magnetic moments, theyare not more than4.00μB. At the same time, we found that for the clusters with the atomnumber from2to8, the magnetic moments increase in an alternating fashion. As the numberof the atom increase, an even-odd alternation between0.00μBand1.00μBwas found over therange n=9to n=20for the Lu_ncluster. A shift from ferromagnetic to ferrimagnetic orderingappears at n=5. These results provide theory assist for study the structure evolution fromcluster to bulk solids, and the magnetism and electronic properties of transition metal cluster.
(2) After doping with single3d transition metal atom M (M=Mn，Fe，Co and Ni) in thetype I Si clathrates, the electronic structure and magnetic properties have changed evident.Compared with pure Si_(46), the constant of crystal lattice in unit cell ofMSiα46andMSiβ46have a decrescence tend. Some of the silicon clathrates with a Mn or Co dopant at the centersite of a Si20cage, or a Mn, Fe or Ni dopant at the center site of a Si24cage are found to behalf-metallic materials with large magnetic moments. For Mn，Fe，Co and Ni dopant, theyhave5.00μB,4.00μB,3.00μBand2.00μBmagnetic moment, respectively. For the silicon clathrates with a Fe or Ni dopant at the center site of a Si20cage or a Co dopant at the centersite of a Si24cage display semi-metallic characters. They also have large magnetic moments.For Fe，Co and Ni dopant, they have4.00μB,3.00μBand2.00μBmagnetic moment,respectively. These results show that MSi_(46)is a fine spintronics material.
(3) When the Eu@C_(60)monolayer adsorbed on the Ag(111) surface, the Eu@C_(60)monolayer induces a substrate reconstruction, the perpendicular distances between theEu@C_(60)and Ag(111) surface is smaller than that between C_(60)and Ag(111) surface by0.05.The Eu@C_(60)monolayer has the same geometry structure as that of C_(60)monolayer on Ag(111)surface. The stable structure with one hexagon of Eu@C_(60)face down and its mirror plane faceparallels to the substrate. The Eu@C_(60)/Ag(111) in unit cell has a big magnetic moment of6.80μB, which mainly come from the Eu atom according to the Mülliken charge populationanalysis. There is no chemical bonds formed between the Eu@C_(60)and Ag (111), only0.55echarge transferred from Ag (111) to Eu@C_(60). These results provide theory assist for study theendohedral fullerenes.
(1)对于Lu_n(n=2-20)团簇，原子数小于16时Lu_n(n＜16)，它们的生长模式都是基于八面体的结构；当原子数大于16时，Lu_n(16≤n≤20)团簇出现了一个新的基于十面体的生长模式。Lu_4，Lu_8，Lu_(13)和Lu_(18)团簇具有较高的稳定性，它们的结合能比相应的相邻原子数Lu团簇的结合能要低。Lu_n(n=2-20)团簇的磁矩较小，都不超过4.00μB。当原子数n=2-8时，Lu_n团簇的磁矩交替增大，随原子数的增大，当n=9-20时，Lu_n团簇的磁矩出现了在0.00μB和1.00μB之间的奇偶交替现象。在原子数n=5处，Lu团簇的磁序发生转变，从铁磁性转变为亚铁磁性。这些结果为研究过渡金属从团簇转变到大块固体的结构演化，以及过渡金属团簇的磁性和电子结构提供了理论依据。
(2)在第一类Si插合物的硅二十笼子或者硅二十四笼子中心掺入单个3d过渡金属原子M(M=Mn，Fe，Co和Ni)后，硅插合物在电子结构和磁性上都出现了明显的变化。与未掺杂的Si_(46)插合物单胞相比，掺杂后MSiα46和MSiβ46的晶格常数均变小。当在硅二十笼子中心掺入Mn或者Co，以及在硅二十四笼子中心掺入Mn，Fe或者Ni原子后，形成的新的插合化合物都表现出half-metallic性质，并且均具有较大的磁矩。Mn，Fe，Co和Ni掺杂后，自旋磁矩分别为5.00μB，4.00μB，3.00μB和2.00μB。而当在硅二十笼子中心掺入Fe或者Ni，以及在硅二十四笼子中心掺入Co原子后，形成的新的插合化合物都表现出了semi-metallic性质，且具有较大的磁矩。Fe，Co和Ni掺杂后分别具有4.00μB，3.00μB和2.00μB的自旋磁矩。以上结果表明，MnSi_(46)是一个较好的半金属材料，将来可能被用于自旋电子学材料。
(3)当Eu@C_(60)单分子层吸附在Ag(111)面上时，我们发现Eu@C_(60)单分子层引起了Ag(111)表面的重构，Eu@C_(60)和Ag(111)之间的垂直距离要比C_(60)和Ag(111)之间的垂直距离要小0.05。在Ag(111)面上Eu@C_(60)单分子层的几何结构和C_(60)单分子层吸附在Ag(111)面上的几何结构相一致。其稳定结构为Eu@C_(60)的一个六边形的面朝向基底，而和这个六边形面相对的另外一个六边形面平行于基底。Eu@C_(60)/Ag(111)单胞具有较大的自旋磁矩，其大小为6.80μB，通过密立根电荷分析我们知道这个较大磁矩主要来源于Eu原子。Eu@C_(60)和Ag(111)之间没有形成较强的化学键，只有0.55e大小的电荷从Ag(111)中转移到了Eu@C_(60)之上。我们的研究结果为C_(60)富勒烯内包物的应用提供了理论依据。
Clusters with nano-scale, fullerenes and spintronics materials have attracted considerableinteresting, for there special geometry structure, novel electronic structure and magnetismproperties. They are promising materials for applications in small spintronics materials. Withthe improvement of density functional theory and the performanc of computer, the firstprinciples calculations based on density functional theory have been applied to the study ofnew materials. In this paper, using density functional theory, we have calculated the structure,electronic and magnetism properties of Lu_n(n=2-20) cluster,3d transition metal-doped type ISi clathrates MSi_(46)(M=Mn，Fe，Co，Ni) and Eu@C_(60)monolayer adsorbed on the surface ofAg(111). The results are as follows:
(1) For Lu_n(n=2-20) cluster, when the number of atoms are smaller than16, the growthpattern of Lu_n(n＜16) cluster are based on octahedral; when the number of atoms are morethan16, the Lu_n(16≤n≤20) cluster have a new growth pattern that based on decahedral. TheLu_4，Lu_8，Lu_(13)and Lu_(18)clusters have higher stability, their binding energise are lower thenthat of their neighbors. All the Lu_n(n=2-20) clusters has small spin magnetic moments, theyare not more than4.00μB. At the same time, we found that for the clusters with the atomnumber from2to8, the magnetic moments increase in an alternating fashion. As the numberof the atom increase, an even-odd alternation between0.00μBand1.00μBwas found over therange n=9to n=20for the Lu_ncluster. A shift from ferromagnetic to ferrimagnetic orderingappears at n=5. These results provide theory assist for study the structure evolution fromcluster to bulk solids, and the magnetism and electronic properties of transition metal cluster.
(2) After doping with single3d transition metal atom M (M=Mn，Fe，Co and Ni) in thetype I Si clathrates, the electronic structure and magnetic properties have changed evident.Compared with pure Si_(46), the constant of crystal lattice in unit cell ofMSiα46andMSiβ46have a decrescence tend. Some of the silicon clathrates with a Mn or Co dopant at the centersite of a Si20cage, or a Mn, Fe or Ni dopant at the center site of a Si24cage are found to behalf-metallic materials with large magnetic moments. For Mn，Fe，Co and Ni dopant, theyhave5.00μB,4.00μB,3.00μBand2.00μBmagnetic moment, respectively. For the silicon clathrates with a Fe or Ni dopant at the center site of a Si20cage or a Co dopant at the centersite of a Si24cage display semi-metallic characters. They also have large magnetic moments.For Fe，Co and Ni dopant, they have4.00μB,3.00μBand2.00μBmagnetic moment,respectively. These results show that MSi_(46)is a fine spintronics material.
(3) When the Eu@C_(60)monolayer adsorbed on the Ag(111) surface, the Eu@C_(60)monolayer induces a substrate reconstruction, the perpendicular distances between theEu@C_(60)and Ag(111) surface is smaller than that between C_(60)and Ag(111) surface by0.05.The Eu@C_(60)monolayer has the same geometry structure as that of C_(60)monolayer on Ag(111)surface. The stable structure with one hexagon of Eu@C_(60)face down and its mirror plane faceparallels to the substrate. The Eu@C_(60)/Ag(111) in unit cell has a big magnetic moment of6.80μB, which mainly come from the Eu atom according to the Mülliken charge populationanalysis. There is no chemical bonds formed between the Eu@C_(60)and Ag (111), only0.55echarge transferred from Ag (111) to Eu@C_(60). These results provide theory assist for study theendohedral fullerenes.
引文
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