Crystal-liquid duality driven ultralow two-channel thermal conductivity in -MgAgSb

Li, J.*; Li, X.*; Zhang, Y.*; Zhu, J.*; Zhao, E.*; 古府 麻衣子; 中島 健次; Avdeev, M.*; Liu, P.-F.*; Sui, J.*; et al.

Applied Physics Reviews (Internet), 11(1), p.011406_1 - 011406_8, 2024/03

https://doi.org/10.1063/5.0173680

The desire for intrinsically low lattice thermal conductivity () in thermoelectrics motivates numerous efforts on understanding the microscopic mechanisms of heat transport in solids. Here, based on theoretical calculations, we demonstrate that -MgAgSb hosts low-energy localized phonon bands and avoided crossing of the rattler modes, which coincides with the inelastic neutron scattering result. Using the two-channel lattice dynamical approach, we find, besides the conventional contribution (70% at 300 K) from particlelike phonons propagating, the coherence contribution dominated by the wavelike tunneling of phonons accounts for 30% of total at 300 K. By considering dual contributions, our calculated room-temperature of 0.64 WmK well agrees with the experimental value of 0.63 WmK. More importantly, our computations give a nonstandard dependence, perfectly explaining the abnormal temperature-trend of in experiment for -MgAgSb. By molecular dynamics simulation, we reveal that the structure simultaneously has soft crystalline sublattices with the metavalent bonding and fluctuating liquid-like sublattices with thermally induced large amplitude vibrations. These diverse forms of chemical bonding arouse mixed part-crystal part-liquid state, scatter strongly heat-carrying phonons, and finally produce extremely low . The fundamental research from this study will accelerate the design of ultralow- materials for energy-conversion applications.

Extreme phonon anharmonicity underpins superionic diffusion and ultralow thermal conductivity in argyrodite AgSnSe

Ren, Q.*; Gupta, M. K.*; Jin, M.*; Ding, J.*; Wu, J.*; Chen, Z.*; Lin, S.*; Fabelo, O.*; Rodriguez-Velamazan, J. A.*; 古府 麻衣子; et al.

Nature Materials, 22, p.999 - 1006, 2023/05

https://doi.org/10.1038/s41563-023-01560-x

Ultralow thermal conductivity and fast ionic diffusion endow superionic materials with excellent performance both as thermoelectric converters and as solid-state electrolytes. Yet the correlation and interdependence between these two features remain unclear owing to a limited understanding of their complex atomic dynamics. Here we investigate ionic diffusion and lattice dynamics in argyrodite AgSnSe using synchrotron X-ray and neutron scattering techniques along with machine-learned molecular dynamics. We identify a critical interplay of the vibrational dynamics of mobile Ag and a host framework that controls the overdamping of low-energy Ag-dominated phonons into a quasi-elastic response, enabling superionicity. Concomitantly, the persistence of long-wavelength transverse acoustic phonons across the superionic transition challenges a proposed 'liquid-like thermal conduction' picture. Rather, a striking thermal broadening of low-energy phonons, starting even below 50 K, reveals extreme phonon anharmonicity and weak bonding as underlying features of the potential energy surface responsible for the ultralow thermal conductivity ( 0.5 WmK) and fast diffusion. Our results provide fundamental insights into the complex atomic dynamics in superionic materials for energy conversion and storage.

Weyl-Kondo semimetal behavior in the chiral structure phase of CeRhSn

岩佐 和晃*; Suyama, Kazuya*; 河村 聖子; 中島 健次; Raymond, S.*; Steffens, P.*; Yamada, Akira*; 松田 達磨*; Aoki, Yuji*; 川崎 郁斗; et al.

Physical Review Materials (Internet), 7(1), p.014201_1 - 014201_11, 2023/01

https://doi.org/10.1103/PhysRevMaterials.7.014201

The spin dynamics, crystalline-electric-field (CEF) level scheme, specific heat, and X-ray photoemission spectra (XPS) of CeRhSn were investigated, which exhibits anomalous semimetal transport in the chiral crystallographic phase. CEF excitations observed at approximately 7 and 39 meV are consistent with the two inequivalent Ce-ion cites in the chiral structure. Because of broader CEF excitations and a strong 4 peak at the Fermi level in the Ce 4 on-resonance spectrum, the hybridized Ce 4 electrons contribute to the semimetal carriers. In addition, the spin fluctuation associated with the Kramers doublet ground state is characterized by the peak located at 0.15 meV. The electronic state involving the spin fluctuation causes the behavior of specific heat below 0.6 K, which is attributed to linear dispersion relations of electrons of the Weyl Kondo semimetal in the chiral-lattice symmetry.

-dependent collective relaxation dynamics of glass-forming liquid CaK(NO) investigated by wide-angle neutron spin-echo

Luo, P.*; Zhai, Y.*; Falus, P.*; Garca Sakai, V.*; Hartl, M.*; 古府 麻衣子; 中島 健次; Faraone, A.*; Z, Y.*

Nature Communications (Internet), 13, p.2092_1 - 2092_9, 2022/04

https://doi.org/10.1038/s41467-022-29778-4

The relaxation behavior of glass formers exhibits spatial heterogeneity and dramatically changes upon cooling towards the glass transition. However, the underlying mechanisms of the dynamics at different microscopic length scales are not fully understood. We measured the -dependent coherent intermediate scattering function of a prototypical ionic glass former CaK(NO), in the highly viscous liquid state. In contrast to the structure modulated dynamics for 2.4 , i.e., at and below the structure factor main peak, for 2.4 , beyond the first minimum above the structure factor main peak, the stretching exponent exhibits no temperature dependence and concomitantly the relaxation time shows smaller deviations from Arrhenius behavior. This finding indicates a change in the dominant relaxation mechanisms around a characteristic length of 2.6 AA, below which the relaxation process exhibits a temperature independent distribution and more Arrhenius-like behavior.

Enhanced covalency and nanostructured-phonon scattering lead to high thermoelectric performance in -type PbS

Rathore, E.*; Juneja, R.*; Sarkar, D.*; Roychowdhury, S.*; 古府 麻衣子; 中島 健次; Singh, A. K.*; Biswas, K.*

Materials Today Energy (Internet), 24, p.100953_1 - 100953_9, 2022/03

https://doi.org/10.1016/j.mtener.2022.100953

We demonstrate a high thermoelectric figure of merit (zT) of 1.45 at 900 K for Ge doped (4-10 mol%) -type PbS, which is the one of the highest values among all -type PbS-based thermoelectric materials. This high performance is achieved by simultaneous (a) enhancement of covalency in chemical bonding which increases the electrical conductivity, and (b) reduction of lattice thermal conductivity to an ultra-low value of 0.56 W mK at 900 K by the introduction of nanometer-sized (5-10 nm) precipitates of PbGeS in PbS matrix which strongly scatter the heat-carrying phonons. The presence of low-lying transverse acoustic (TA) and longitudinal acoustic (LA) phonon modes at 48.24 cm and 91.83 cm, respectively are experimentally revealed from inelastic neutron scattering (INS) experiments. The softening of low-frequency modes at a higher temperature and ultra-short phonon lifetime (1-4.5 ps) further explain the ultra-low thermal conductivity.

Magnons and spinons in BaCoTeO; A Composite system of isolated spin- triangular Heisenberg-like and frustrated honeycomb Ising-like antiferromagnets

児島 佑樹*; 栗田 伸之*; 田中 秀数*; 中島 健次

Physical Review B, 105(2), p.L020408_1 - L020408_6, 2022/01

https://doi.org/10.1103/PhysRevB.105.L020408

二次元性の良いスピン1/2Heisenberg三角格子反強磁性体を含むBaCoTeOの磁気励起を中性子散乱を用いて観測した。BaCoTeOの磁気モデルは2つの独立した二次元系スピン1/2Heisenberg三角格子反強磁性体とIsing的J1-J2-J3ハニカム格子反強磁性体で捉えることができる。三角格子に由来する励起スペクトルは線形スピン波理論の分散関係とは異なり、複数のロトンライクミニマムを持つ。これはフェルミオニックスピノンを用いた計算によって示される結果と類似している。ハニカム格子に由来する分散関係は高エネルギー領域に現われ、線形スピン波理論で捉えることができた。

Dimensional reduction by geometrical frustration in a cubic antiferromagnet composed of tetrahedral clusters

大熊 隆太郎*; 古府 麻衣子; 浅井 晋一郎*; Avdeev, M.*; 幸田 章宏*; 岡部 博孝*; 平石 雅俊*; 竹下 聡史*; 小嶋 健児*; 門野 良典*; et al.

Nature Communications (Internet), 12, p.4382_1 - 4382_7, 2021/07

https://doi.org/10.1038/s41467-021-24636-1

Dimensionality is a critical factor in determining the properties of solids and is an apparent built- in character of the crystal structure. However, it can be an emergent and tunable property in geometrically frustrated spin systems. Here, we study the spin dynamics of the tetrahedral cluster antiferromagnet, pharmacosiderite, via muon spin resonance and neutron scattering. We find that the spin correlation exhibits a two-dimensional characteristic despite the isotropic connectivity of tetrahedral clusters made of spin 5/2 Fe ions in the three-dimensional cubic crystal, which we ascribe to two-dimensionalisation by geometrical frustration based on spin wave calculations. Moreover, we suggest that even one-dimensionalisation occurs in the decoupled layers, generating low-energy and one-dimensional excitation modes, causing large spin fluctuation in the classical spin system.

Mode distribution analysis for superionic melt of CuI by coherent quasielastic neutron scattering

川北 至信; 菊地 龍弥*; 田原 周太*; 中村 充孝; 稲村 泰弘; 丸山 健二*; 山内 康弘*; 河村 聖子; 中島 健次

JPS Conference Proceedings (Internet), 33, p.011071_1 - 011071_6, 2021/03

BB2019-1144.pdf:0.7MB

https://doi.org/10.7566/JPSCP.33.011071

ヨウ化銅は高温固相で、ヨウ素イオンが作る面心立方格子の隙間を銅イオンが動く超イオン伝導体になることで知られている。溶融相でも、集団的あるいは協調的なイオンの運動を示す特徴がある。MDシミュレーションにおいて、銅イオンの拡散がヨウ素イオンより非常に速いこと分かっている。Cu-Cu部分構造因子にはFSDPと呼ばれる構造を持ち、銅の分布に中距離秩序があることを示している。さらに、Cu-Cu部分二体分布関数は、Cu-Iで形成される最近接分布に深く入り込んでいる。そうした溶融CuIの異常的振る舞いの原因を解明するために、J-PARCの物質・生命科学実験施設に設置されたディスクチョッパー分光器AMATERASを用いて、中性子準弾性散乱(QENS)実験を行った。構造可干渉性のQENSから得られた動的構造因子を理解するため、モード分布解析を行った。その結果、ヨウ素イオンの運動が局所的に閉じ込められた空間で揺らぐような運動であること、一方銅イオンはヨウ素イオンより速く拡散する運動をしていることが分かった。

Sequence-dependent hydration water dynamics of dodecameric DNA

中川 洋; 米谷 佳晃*; 中島 健次; 河村 聖子; 菊地 龍弥*; 稲村 泰弘; 片岡 幹雄*; 河野 秀俊*

JPS Conference Proceedings (Internet), 33, p.011101_1 - 011101_6, 2021/03

https://doi.org/10.7566/JPSCP.33.011101

5'CGCGCGCG'3 and 5'CGCGCGCG'3のDNAについて、軽水と重水のコントラストを利用した中性子準弾性散乱による水和水ダイナミクスを測定した。この2つのDNAは計算機によってそれぞれ硬い分子と柔らかい分子であることが分かっている。どちらの配列も約240KにDNAと水和水のどちらも動力学転移が観測された。転移温度以上では、水和水の平均自乗変位は硬い配列の方が小さかった。また水和水の緩和時間は硬いほうが長かった。ピコ秒時間スケールの水和水ダイナミクスは配列依存的なDNAの硬さと関係していることを示唆した。

Relevance of hydrogen bonded associates to the transport properties and nanoscale dynamics of liquid and supercooled 2-propanol

Zhai, Y.*; Luo, P.*; 長尾 道弘*; 中島 健次; 菊地 龍弥*; 川北 至信; Kienzle, P. A.*; Z, Y.*; Faraone, A.*

Physical Chemistry Chemical Physics, 23(12), p.7220 - 7232, 2021/03

https://doi.org/10.1039/d0cp05481j

2-Propanol was investigated, in both the liquid and supercooled states, as a model system to study how hydrogen bonds affect the structural relaxation and the dynamics of mesoscale structures, of approximately several Angstroms, employing static and quasi-elastic neutron scattering and molecular dynamics simulation. Dynamic neutron scattering measurements were performed over an exchanged wave-vector range encompassing the pre-peak, indicative of the presence of H-bonding associates, and the main peak. The dynamics observed at the pre-peak is associated with the formation and disaggregation of the H-bonded associates and is measured to be at least one order of magnitude slower than the dynamics at the main peak, which is identified as the structural relaxation. The measurements indicate that the macroscopic shear viscosity has a similar temperature dependence as the dynamics of the H-bonded associates, which highlights the important role played by these structures, together with the structural relaxation, in defining the macroscopic rheological properties of the system. Importantly, the characteristic relaxation time at the pre-peak follows an Arrhenius temperature dependence whereas at the main peak it exhibits a non-Arrhenius behavior on approaching the supercooled state. The origin of this differing behavior is attributed to an increased structuring of the hydrophobic domains of 2-propanol accommodating a more and more encompassing H-bond network, and a consequent set in of dynamic cooperativity.