Strong low-energy rattling modes enabled liquid-like ultralow thermal conductivity in a well-ordered solid

Liu, P.-F.*; Li, X.*; Li, J.*; Zhu, J.*; Tong, Z.*; 古府 麻衣子*; 楡井 真実; Xu, J.*; Yin, W.*; Wang, F.*; et al.

National Science Review, 11(12), p.nwae216_1 - nwae216_10, 2024/12

https://doi.org/10.1093/nsr/nwae216

Crystalline solids exhibiting inherently low lattice thermal conductivity () are of great importance in applications such as thermoelectrics and thermal barrier coatings. However, cannot be arbitrarily low and is limited by the minimum thermal conductivity related to phonon dispersions. In this work, we report the liquid-like thermal transport in a well-ordered crystalline CsAgTe, which exhibits an extremely low value of 0.18 WmK. On the basis of first-principles calculations and inelastic neutron scattering measurements, we find that there are lots of low-lying optical phonon modes at 3.1 meV hosting the avoided-crossing behavior with acoustic phonons. These strongly localized modes are accompanied by weakly bound rattling Ag atoms with thermally induced large amplitudes of vibrations. Using the two-channel model, we demonstrate that coupling of the particle-like phonon modes and the heat-carrying wave-like phonons is essential for understanding the low , which is heavily deviated from the temperature dependence of the standard Peierls theory. In addition, our analysis indicates that the soft structural framework with liquid-like motions of the fluctuating Ag atoms is the underlying cause that leads to the suppression of the heat conduction in CsAgTe. These factors synergistically account for the ultralow value. Our results demonstrate that the liquid-like heat transfer could indeed exist in a well-ordered crystal.

Brightening triplet excitons enable high-performance white-light emission in organic small molecules via integrating n-- transitions

Yang, Q.*; Yang, X.*; Wang, Y.*; Fei, Y.*; Li, F.*; Zheng, H.*; Li, K.*; Han, Y.*; 服部 高典; Zhu, P.*; et al.

Nature Communications (Internet), 15, p.7778_1 - 7778_9, 2024/09

https://doi.org/10.1038/s41467-024-52196-7

明るい一重項励起子と三重項励起子を同時に発現する発光材料は、オプトエレクトロニクス、サイネージ、情報暗号化において大きな可能性を秘めている。しかしながら、高性能の白色発光を実現するためには、蛍光と燐光の寄与が不均衡であることが大きな障害となっている。ここでは、水素結合の協同効果による圧力処理エンジニアリングによって、n--遷移の混合を実現し、イソフタル酸(IPA)中で三重項状態の発光を7%から40%に高めることで、この課題に対処した。加圧処理したIPAでは、蛍光と燐光のハイブリッドに基づく優れた白色発光が得られ、フォトルミネッセンス量子収率は当初の19%(青色発光)から75%に増加した。その場での高圧IRスペクトル、X線回折、中性子回折から、圧力の上昇に伴い水素結合が連続的に強化されることが明らかになった。さらに、この強化された水素結合は、圧力処理後も常圧条件下まで保持され、バランスの取れた一重項/三重項励起子集団のための効率的な系間交差を目的としたIPAに与え、効率的な白色発光をもたらした。この研究は、有機低分子の三重項状態を明るくするルートを提案するだけでなく、一重項励起子と三重項励起子の比率を調節して、高性能の白色発光を構築するものである。

Microscopic insights of the extraordinary work-hardening due to phase transformation

Ma, Y.*; Naeem, M.*; Zhu, L.*; He, H.*; Sun, X.*; Yang, Z.*; He, F.*; Harjo, S.; 川崎 卓郎; Wang, X.-L.*

Acta Materialia, 270, p.119822_1 - 119822_13, 2024/05

https://doi.org/10.1016/j.actamat.2024.119822

We report an in situ neutron diffraction study of 316 L that reveals an extraordinary work-hardening rate (WHR) of 7 GPa at 15 K. Detailed analyses show that the major contribution to the excellent strength and ductility comes from the transformation-induced plasticity (TRIP) effect, introduced by the austenite-to-martensite (-to-') phase transition. A dramatic increase in the WHR is observed along with the transformation; the WHR declined when the austenite phase is exhausted. During plastic deformation, the volume-fraction weighted phase stress and stress contribution from the '-martensite increase significantly. The neutron diffraction data further suggest that the -to-' phase transformation was mediated by the -martensite, as evidenced by the concurrent decline of the phase with the phase.

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.

decay of exotic P and S isotopes with neutron number near 28

Tripathi, V.*; Bhattacharya, S.*; Rubino, E.*; Benetti, C.*; Perello, J. F.*; Tabor, S. L.*; Liddick, S. N.*; Bender, P. C.*; Carpenter, M. P.*; Carroll, J. J.*; et al.

Physical Review C, 106(6), p.064314_1 - 064314_14, 2022/12

https://doi.org/10.1103/PhysRevC.106.064314

ミシガン州立大学の国立超伝導サイクロトロン研究所にて、中性子過剰なリン、硫黄同位体を生成し、そこからのベータ崩壊半減期および娘核の励起準位を測定した。Pの崩壊によって得られるエネルギー準位から、この原子核の基底状態はあるいはであることが示唆された。中性子数が偶数の硫黄同位体からの崩壊様式を系統的に調べた結果、中性子数が増えるにつれてガモフテラー遷移強度の大きな準位の励起エネルギーが高くなることがわかった。これは、大規模殻模型計算によって予言されている現象に一致する。

Martensitic transformation in CrCoNi medium-entropy alloy at cryogenic temperature

Naeem, M.*; Zhou, H.*; He, H.*; Harjo, S.; 川崎 卓郎; Lan, S.*; Wu, Z.*; Zhu, Y.*; Wang, X.-L.*

Applied Physics Letters, 119(13), p.131901_1 - 131901_7, 2021/09

https://doi.org/10.1063/5.0067268

We investigated the in situ deformation behavior of the CrCoNi medium-entropy alloy at a cryogenic temperature of 140 K and compared it with deformation at room temperature. The sample exhibited higher strength and larger ductility at the cryogenic temperature. The CrCoNi alloy remained single-phase face-centered cubic at room temperature, while deformation at 140 K resulted in a martensitic transformation to the hexagonal close-packed structure. The phase transformation, an additional deformation mechanism to stacking faults, twinning, and dis- location slip, resulted in a higher work hardening at cryogenic temperature. The study addresses the structure metastability in the CrCoNi alloy, which led to the formation of epsilon-martensite from the intrinsic stacking faults.

Ultra-fine CeO particles triggered strong interaction with LaFeO framework for total and preferential CO oxidation

Zheng, Y.*; Xiao, H.*; Li, K.*; Wang, Y.*; Li, Y.*; Wei, Y.*; Zhu, X.*; Li, H.-W.*; 松村 大樹; Guo, B.*; et al.

ACS Applied Materials & Interfaces, 12(37), p.42274 - 42284, 2020/09

https://doi.org/10.1021/acsami.0c10271

Interactions between the active components with the support are one of the fundamentally factors in determining the catalytic performance of a catalyst. In this study, we investigated the interaction between CeO and LaFeO, the two important oxygen storage materials in catalysis area, by tuning the sizes of CeO particles and highlight a two-fold effect of the strong oxide-oxide interaction in determining the catalytic activity and selectivity for preferential CO oxidation in hydrogen feeds. It is found that the anchoring of ultra-fine CeO particles at the framework of three-dimensional-ordered macroporous LaFeO surface results in a strong interaction between the two oxides that induces the formation of abundant uncoordinated cations and oxygen vacancy at the interface. This discovery demonstrates that in hybrid oxide-based catalysts, tuning the interaction among different components is essential for balancing the catalytic activity and selectivity.

Second-order structural transition in the superconductor LaCoSn

Cheung, Y. W.*; Zhang, J. Z.*; Zhu, J. Y.*; Yu, W. C.*; Hu, Y. J.*; Wang, D. G.*; 大友 優香*; 岩佐 和晃*; 金子 耕士; 今井 正樹*; et al.

Physical Review B, 93(24), p.241112_1 - 241112_5, 2016/06

AA2016-0058.pdf:0.95MB

https://doi.org/10.1103/PhysRevB.93.241112

The quasi-skutterudite superconductor LaCoSn undergoes a phase transition at = 152 K. By measuring the temperature dependence of heat capacity, electrical resistivity, and the superlattice reflection intensity using X-ray, we explore the character of the phase transition at . Our lattice dynamic calculations found imaginary phonon frequencies around the point, when the high temperature structure is used in the calculations, indicating that the structure is unstable at the zero temperature limit. The combined experimental and computational results establish that is associated with a second-order structural transition with = (0.5, 0.5, 0) (or the point). Further electronic band structure calculations reveal Fermi surface sheets with low-curvature segments, which allow us to draw qualitative comparison with both SrIrSn and SrRhSn in which similar physics has been discussed recently.

Spectroscopic evidence of band Jahn-Teller distortion upon martensitic phase transition in Heusler-type Ni-Fe(Co)-Ga ferromagnetic shape-memory alloy films

角田 一樹*; 白井 開渡*; Zhu, S.-Y.*; 谷口 雅樹*; Ye, M.*; 上田 茂典*; 竹田 幸治; 斎藤 祐児; Aseguinolaza, I. R.*; Barandiarn, J. M.*; et al.

Physical Review B, 91(13), p.134417_1 - 134417_6, 2015/04

https://doi.org/10.1103/PhysRevB.91.134417

The temperature evolution of the electronic structure of a Ni-Fe(Co)-Ga/MgO(100), Heusler-type, ferromagnetic shape-memory alloy thin film has been followed by a bulk-sensitive hard X-ray photoelectron spectroscopy, element-selective soft X-ray magnetic circular dichroism, and first-principles calculation. The reversible changes of the electronic states near the Fermi energy show a hysteresis associated with the martensitic phase transition (MPT), where the pseudogap opens on cooling and closes again on warming. In addition, the Ni 3d spin magnetic moment increases by approximately two times across the MPT, whereas the change of Fe 3d moment is moderate. By comparing the experimental results with the calculated spin-resolved density of states, we conclude that the band Jahn-Teller effect of Ni 3d and Fe 3d orbitals is responsible for MPT.

Diluted ferromagnetic semiconductor Li(Zn,Mn)P with decoupled charge and spin doping

Deng, Z.*; Zhao, K.*; Gu, B.; Han, W.*; Zhu, J. L.*; Wang, X. C.*; Li, X.*; Liu, Q. Q.*; Yu, R. C.*; 後神 達郎*; et al.

Physical Review B, 88(8), p.081203_1 - 081203_5, 2013/08

https://doi.org/10.1103/PhysRevB.88.081203

We report the discovery of a diluted magnetic semiconductor, Li(Zn,Mn)P, in which charge and spin are introduced independently via lithium off-stoichiometry and the isovalent substitution of Mn for Zn, respectively. Isostructural to (Ga,Mn)As, Li(Zn,Mn)P was found to be a -type ferromagnetic semiconductor with excess lithium providing charge doping. First-principles calculations indicate that excess Li is favored to partially occupy the Zn site, leading to hole doping. Ferromagnetism with Curie temperature up to 34 K is achieved while the system still shows semiconducting transport behavior.