skip to main content


Title: Structural and thermal properties of Eu 2 Ga 11 Sn 35
Clathrates have been reported to form in a variety of different structure types; however, inorganic clathrate-I materials with a low-cation concentration have yet to be investigated. Furthermore, tin-based compositions have been much less investigated as compared to silicon or germanium analogs. We report the temperature-dependent structural and thermal properties of single-crystal Eu 2 Ga 11 Sn 35 revealing the effect of structure and composition on the thermal properties of this low-cation clathrate-I material. Specifically, low-temperature heat capacity, thermal conductivity, and synchrotron single-crystal x-ray diffraction reveal a departure from Debye-like behavior, a glass-like phonon mean-free path for this crystalline material, and a relatively large Grüneisen parameter due to the dominance of low-frequency Einstein modes. Our analyses indicate thermal properties that are a direct result of the structure and composition of this clathrate-I material.  more » « less
Award ID(s):
1834750 1748188
NSF-PAR ID:
10400547
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Journal of Applied Physics
Volume:
133
Issue:
9
ISSN:
0021-8979
Page Range / eLocation ID:
095108
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. High occupancy of cation sites is typical for clathrate-I compositions allowing limited tunability of the electrical properties beyond doping and elemental substitution. Herein, we report on the structure and electrical transport of single-crystal Eu 2 Ga 11 Sn 35 , the sole example of a very low (25%) cation concentration clathrate-I material with atypical transport directly attributable to the structure and stoichiometry. 
    more » « less
  2. Abstract

    The compositional screening of K‐Zn‐Sb ternary system aided by machine learning, rapid exploratory synthesis using KH salt‐like precursor and in situ powder X‐ray diffraction yielded a novel clathrate type XI K58Zn122Sb207. This clathrate consists of a 3D Zn‐Sb framework hosting K+ions inside polyhedral cages, some of which are reminiscent of known clathrate types while others are unique to this structure type. The complex non‐centrosymmetric structure in the tetragonal space groupwas solved by means of single crystal X‐ray diffraction as a 6‐component twin due to pseudocubic symmetry and further confirmed by high‐resolution synchrotron powder X‐ray diffraction and state‐of‐the‐art scanning transmission electron microscopy. The electron‐precise composition of this clathrate yields narrow‐gapp‐type semiconductor with extraordinarily low thermal conductivity due to displacement or “rattling” of K cations inside oversized cages and as well as to twinning, stacking faults and antiphase boundary defects.

     
    more » « less
  3. Abstract

    The compositional screening of K‐Zn‐Sb ternary system aided by machine learning, rapid exploratory synthesis using KH salt‐like precursor and in situ powder X‐ray diffraction yielded a novel clathrate type XI K58Zn122Sb207. This clathrate consists of a 3D Zn‐Sb framework hosting K+ions inside polyhedral cages, some of which are reminiscent of known clathrate types while others are unique to this structure type. The complex non‐centrosymmetric structure in the tetragonal space groupwas solved by means of single crystal X‐ray diffraction as a 6‐component twin due to pseudocubic symmetry and further confirmed by high‐resolution synchrotron powder X‐ray diffraction and state‐of‐the‐art scanning transmission electron microscopy. The electron‐precise composition of this clathrate yields narrow‐gapp‐type semiconductor with extraordinarily low thermal conductivity due to displacement or “rattling” of K cations inside oversized cages and as well as to twinning, stacking faults and antiphase boundary defects.

     
    more » « less
  4. Single crystals of the quaternary chalcogenide BaCuGdTe 3 were obtained by direct reaction of elements allowing for a complete investigation of the intrinsic electrical and thermal properties of this previously uninvestigated material. The structure was investigated by high-resolution single-crystal synchrotron X-ray diffraction, revealing an orthorhombic crystal structure with the space group Cmcm. Although recently identified as a semiconductor suitable for thermoelectric applications from theoretical analyses, our electrical resistivity and Seebeck coefficient measurements show metallic conduction, the latter revealing strong phonon-drag. Temperature dependent hole mobility reveals dominant acoustic phonon scattering. Heat capacity data reveal a Debye temperature of 183 K and a very high density of states at the Fermi level, the latter confirming the metallic nature of this composition. Thermal conductivity is relatively high with Umklapp processes dominating thermal transport above the Debye temperature. The findings in this work lay the foundation for a more detailed understanding of the physical properties of this and similar multinary chalcogenide materials, and is part of the continuing effort in investigating quaternary chalcogenide materials and their suitability for use in technological applications. 
    more » « less
  5. null (Ed.)
    The unconventional clathrates, Cs 8 Zn 18 Sb 28 and Cs 8 Cd 18 Sb 28 , were synthesized and reinvestigated. These clathrates exhibit unique and extensive superstructural ordering of the clathrate-I structure that was not initially reported. Cs 8 Cd 18 Sb 28 orders in the Ia 3̄ d space group (no. 230) with 8 times larger volume of the unit cell in which most framework atoms segregate into distinct Cd and Sb sites. The structure of Cs 8 Zn 18 Sb 28 is much more complicated, with an 18-fold increase of unit cell volume accompanied by significant reduction of symmetry down to P 2 (no. 3) monoclinic space group. This structure was revealed by a combination of synchrotron X-ray diffraction and electron microscopy techniques. A full solid solution, Cs 8 Zn 18−x Cd x Sb 28 , was also synthesized and characterized. These compounds follow Vegard's law in regard to their primitive unit cell sizes and melting points. Variable temperature in situ synchrotron powder X-ray diffraction was used to study the formation and melting of Cs 8 Zn 18 Sb 28 . Due to the heavy elements comprising clathrate framework and the complex structural ordering, the synthesized clathrates exhibit ultralow thermal conductivities, all under 0.8 W m −1 K −1 at room temperature. Cs 8 Zn 9 Cd 9 Sb 28 and Cs 8 Zn 4.5 Cd 13.5 Sb 28 both have total thermal conductivities of 0.49 W m −1 K −1 at room temperature, among the lowest reported for any clathrate. Cs 8 Zn 18 Sb 28 has typical p-type semiconducting charge transport properties, while the remaining clathrates show unusual n–p transitions or sharp increases of thermopower at low temperatures. Estimations of the bandgaps as activation energy for resistivity dependences show an anomalous widening and then shrinking of the bandgap with increasing Cd-content. 
    more » « less