Devin C. Schmitt

Probing the Lower Limit of Lattice Thermal Conductivity in an Ordered Extended Solid: Gd117Co56Sn112, a Phonon Glass–Electron Crystal System

The discovery of novel materials with low thermal conductivity is paramount to improving the efficiency of thermoelectric devices. As lattice thermal conductivity is inversely linked to unit cell complexity, we set out to synthesize a highly complex crystalline material with glasslike thermal conductivity. Here we present the structure, transport properties, heat capacity, and magnetization of single-crystal Gd(117)Co(56)Sn(112), a complex material with a primitive unit cell volume of ~6858 Å(3) and ~285 atoms per primitive unit cell (1140 atoms per face-centered cubic unit cell). The room temperature lattice thermal conductivity of this material is κ(L) = 0.28 W/(m·K) and represents one of the lowest ever reported for a nonglassy or nonionically conducting bulk solid. Furthermore, this material exhibits low resistivity at room temperature, and thus represents a true physical system that approaches the ideal phonon glass-electron crystal.

Targeted Crystal Growth of Rare Earth Intermetallics with Synergistic Magnetic and Electrical Properties: Structural Complexity to Simplicity

The single-crystal growth of extended solids is an active area of solid-state chemistry driven by the discovery of new physical phenomena. Although many solid-state compounds have been discovered over the last several decades, single-crystal growth of these materials in particular enables the determination of physical properties with respect to crystallographic orientation and the determination of properties without possible secondary inclusions. The synthesis and discovery of new classes of materials is necessary to drive the science forward, in particular materials properties such as superconductivity, magnetism, thermoelectrics, and magnetocalorics. Our research is focused on structural characterization and determination of physical properties of intermetallics, culminating in an understanding of the structure-property relationships of single-crystalline phases. We have prepared and studied compounds with layered motifs, three-dimensional magnetic compounds exhibiting anisotropic magnetic and transport behavior, and complex crystal structures leading to intrinsically low lattice thermal conductivity. In this Account, we present the structural characteristics and properties that are important for understanding the magnetic properties of rare earth transition metal intermetallics grown with group 13 and 14 metals. We present phases adopting the HoCoGa5 structure type and the homologous series. We also discuss the insertion of transition metals into the cuboctahedra of the AuCu3 structure type, leading to the synthetic strategy of selecting binaries to relate to ternary intermetallics adopting the Y4PdGa12 structure type. We provide examples of compounds adopting the ThMn12, NaZn13, SmZn11, CeCr2Al20, Ho6Mo4Al43, CeRu2Al10, and CeRu4Al16-x structure types grown with main-group-rich self-flux methods. We also discuss the phase stability of three related crystal structures containing atoms in similar chemical environments: ThMn12, CaCr2Al10, and YbFe2Al10. In addition to dimensionality and chemical environment, complexity is also important in materials design. From relatively common and well-studied intermetallic structure types, we present our motivation to work with complex stannides adopting the Dy117Co57Sn112 structure type for thermoelectric applications and describe a strategy for the design of new magnetic intermetallics with low lattice thermal conductivity. Our quest to grow single crystals of rare-earth-rich complex stannides possessing low lattice thermal conductivity led us to discover the new structure type Ln30Ru4+xSn31-y (Ln = Gd, Dy), thus allowing the correlation of primitive volumes with lattice thermal conductivities. We highlight the observation that Ln30Ru4+xSn31-y gives rise to highly anisotropic magnetic and transport behavior, which is unexpected, illustrating the need to measure properties on single crystals.

Structural complexity meets transport and magnetic anisotropy in single crystalline Ln30Ru4Sn31 (Ln = Gd, Dy).

We present the structure of Ln(30)Ru(4+x)Sn(31-y) (Ln = Gd, Dy) and the anisotropic resistivity, magnetization, thermopower, and thermal conductivity of single crystal Ln(30)Ru(4+x)Sn(31-y) (Ln = Gd, Tb). Gd(30)Ru(4.92)Sn(30.54) crystallizes in a new structure-type with space group Pnnm and dimensions of a = 11.784(1) Å, b = 24.717(1) Å, and c = 11.651(2) Å, and V = 3394(1) Å(3). Magnetic anisotropy and highly anisotropic electrical transport behavior were observed in the single crystals of Gd(30)Ru(4.92)Sn(30.54) and Tb(30)Ru(6)Sn(29.5). Additionally, the lattice thermal conductivity of Tb(30)Ru(6)Sn(29.5) is quite low, and a comparison is made to other Sn-containing compounds.

Field-pulse memory in a spin-glass

We report a magnetic field-pulse memory effect in the temperature-dependent magnetization of Tb30Ru6.0Sn29.5, a spin-glass material having a newly identified structure type. Tb30Ru6.0Sn29.5 exhibits a glassy magnetization component of ∼2290 emu/mol-Tb, which represents over 84% of its total saturation magnetization. We show that when a magnetic field pulse of a few hundred gauss is applied to the sample as it is cooling, the system retains a memory of the temperature at which the pulse was applied. Upon warming, the imprinted memory is observed as a precipitous drop in magnetization at the pulse temperature.

Investigation of Fe incorporation in LnCr2Al20 (Ln = La, Gd, Yb) with 57Fe Mössbauer and single crystal X-ray diffraction.

Crystal growth, structure determination, and magnetic properties of LnCr2Al(20-x)Fe(x) (Ln = La, Gd, Yb) adopting the CeCr2Al20 structure type with space group Fd3m, a ∼ 14.5 Å, are reported. Single crystal X-ray diffraction and Mössbauer spectroscopy are employed to fully characterize the crystal structure of LnCr2Al(20-x)Fe(x) (Ln = La, Gd, Yb). LnCr2Al(20-x)Fe(x) (Ln = La, Gd, Yb) are the first pseudoternaries adopting the CeCr2Al20 structure type with a transition metal occupying the main group site. The Yb analogues are Pauli paramagnets with the Yb ion adopting an electronic configuration close to Yb(2+), while the Gd analogues show paramagnetic behavior with no magnetic order down to 3 K.

3-(Trimethyl-sil-yl)prop-2-ynyl p-toluene-sulfonate.

In the title compound, C13H18O3SSi, the SO3 group displays a partial rotational (ca 50°) disorder about the C—S bond, with relative proportions 0.7744 (13):0.2256 (13). This disorder also forces the propynyl CH2 group to be disordered.