<p> We investigated the local electronic properties of the triangular-lattice materials NaxCO2 (x = 0.3, 0.72) and the superconductor Na0.3Co02-1.3H20 by 59Co and 170 Nuclear Magnetic Resonance(NMR). For Na0.72Co02 , 59Co NMR line shape shows clearly that there are two types of Co sites - Co(A) site and Co(B) site. The electronic character of Co(A) site is close to that of the less magnetic Co+3-like ion with spin rv 0, while the electronic character of Co(B) site is close to that of the strongly magnetic Co+4-like ions with spin ~ 1/2. The temperature dependence of the Knight shifts suggests that the Co(A) and Co(B) sites are electronically coupled, which is not consistent with simple phase separation. The local Co electronic environments propagate to the adjacent 0 layers through p-d hybridization. Therefore, there are two types of oxygen sites, O(A) site and O(B) site. We introduced a different route to do K vs x plot analysis for the Co sites and determined that for the Co sites, Karbitat(A) is 1.816 % and Kspin(A) is about rv 0.2 %; Karbitat(B) is 4.0255 % and Kspin(B) is at least 1.5 %. For Na0 .3Co02 , 59Co NMR line shape shows that the Co valence is averaged out in this material. There are two types of oxygen sites, 0( C) site and O(D) site, presumably because of the nearest neighbor Na+ sites. The constant behavior of Knight shifts below 100 K for both the Co and 0 sites suggests the emergence of a low temperature canonical Fermi-liquid behavior. For the superconductor Na0.3CoO2-1.3H20, both 59Co and 170 NMR line shapes show that there is only one type of Co site and oxygen site. The Knight shifts of 59Co and 170 are temperature independent below 100 K down to Tc. Combined with our spin-lattice relaxation 1/T 1 T measurements, we can rule out the possibility of ferromagnetic scenario of spin excitations above Tc. </p> / Thesis / Master of Science (MSc)

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22685号 / 理博第4626号 / 新制||理||1665(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 前里 光彦, 教授 吉村 一良, 教授 有賀 哲也 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19479号 / 理博第4139号 / 新制||理||1595(附属図書館) / 32515 / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)准教授 戸塚 圭介, 教授 川上 則雄, 教授 石田 憲二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

In this PhD thesis, the physics of vacancies in two-dimensional ordered Heisenberg antiferromagnets is investigated. We use semi-classical methods to study the influence of a single vacancy in long-range ordered states, with a focus on non-collinear order. Here, on a classical level, a magnetic distortion is created as the spins readjust in response to the vacancy. We use the non-collinear $120^\\circ$ state on the frustrated triangular lattice as an example, where we determine the impurity contributions to the magnetization and susceptibility. An important discovery is the vacancy moment not being quantized due to non-universal partial screening. The resulting effective moment $m_0 \\ll S$ can be observed as a fractional prefactor to an impurity-induced Curie response $m_0^2/(3k_BT)$ at finite temperature. This is in sharp contrast to collinearly ordered states. Here the moment is always quantized to the bulk spin value, $m_0=S$. Furthermore, we present a detailed analysis of the vacancy-induced distortion cloud. Due to Goldstone modes, it decays algebraically as $r^{-3}$ with distance $r$ to the vacancy. Using leading-order $1/S$-expansion, we determine the quantum corrections to both size and direction of the distorted magnetic moments. Secondly, we study the same problem in the presence of an external magnetic field $h$, both for the square and triangular lattice. For the triangular lattice we use a biquadratic exchange term $K$ to stabilize a unique ground state from a degenerate manifold. The finite-field vacancy moment $m(h)$ is generated by field-dependent screening clouds, as different non-collinear bulk states evolve with increasing field. These distortion clouds decay exponentially on a magnetic length scale $l_h\\propto 1/h$. Most importantly, we find that the magnetic-field linear-response limit $h \\rightarrow 0^+$ is generically singular for $SU(2)$ ordered local-moment antiferromagnets, as the vacancy moment in zero field differs fundamentally from even an infinitesimal but finite field, $m(h \\rightarrow 0^+)\\neq m_0$. Moreover, a part of the screening cloud itself becomes universally singular. Particularly for spin-flop states, this leads to a semi-classical version of perfect screening. We present general arguments to support these claims, as well as microscopic calculations. Another remarkable result is an impurity-induced quantum phase transition for overcompensated vacancies in the $M=1/3$ plateau phase on the triangular lattice with $K<0$. We close our analysis with a discussion about important limits for finite vacancy concentrations, as well as a possible experimental verification of our predictions.

This work outlines the numerical strategies for two sets of problems of great importance in correlated materials research. First, we analyze the electronic structure and magnetic properties of 3d transition metals with linear coordination. Second, we study the mutiplet structure of 4f ions arranged on the 2D triangular-lattice.

In this PhD thesis, the physics of vacancies in two-dimensional ordered Heisenberg antiferromagnets is investigated. We use semi-classical methods to study the influence of a single vacancy in long-range ordered states, with a focus on non-collinear order. Here, on a classical level, a magnetic distortion is created as the spins readjust in response to the vacancy. We use the non-collinear $120^\\circ$ state on the frustrated triangular lattice as an example, where we determine the impurity contributions to the magnetization and susceptibility. An important discovery is the vacancy moment not being quantized due to non-universal partial screening. The resulting effective moment $m_0 \\ll S$ can be observed as a fractional prefactor to an impurity-induced Curie response $m_0^2/(3k_BT)$ at finite temperature. This is in sharp contrast to collinearly ordered states. Here the moment is always quantized to the bulk spin value, $m_0=S$. Furthermore, we present a detailed analysis of the vacancy-induced distortion cloud. Due to Goldstone modes, it decays algebraically as $r^{-3}$ with distance $r$ to the vacancy. Using leading-order $1/S$-expansion, we determine the quantum corrections to both size and direction of the distorted magnetic moments. Secondly, we study the same problem in the presence of an external magnetic field $h$, both for the square and triangular lattice. For the triangular lattice we use a biquadratic exchange term $K$ to stabilize a unique ground state from a degenerate manifold. The finite-field vacancy moment $m(h)$ is generated by field-dependent screening clouds, as different non-collinear bulk states evolve with increasing field. These distortion clouds decay exponentially on a magnetic length scale $l_h\\propto 1/h$. Most importantly, we find that the magnetic-field linear-response limit $h \\rightarrow 0^+$ is generically singular for $SU(2)$ ordered local-moment antiferromagnets, as the vacancy moment in zero field differs fundamentally from even an infinitesimal but finite field, $m(h \\rightarrow 0^+)\\neq m_0$. Moreover, a part of the screening cloud itself becomes universally singular. Particularly for spin-flop states, this leads to a semi-classical version of perfect screening. We present general arguments to support these claims, as well as microscopic calculations. Another remarkable result is an impurity-induced quantum phase transition for overcompensated vacancies in the $M=1/3$ plateau phase on the triangular lattice with $K<0$. We close our analysis with a discussion about important limits for finite vacancy concentrations, as well as a possible experimental verification of our predictions.