Beyond Rattling: Tetrahedrites as Incipient Ionic Conductors.

Materials with ultralow thermal conductivity are crucial to many technological applications, including thermoelectric energy harvesting, thermal barrier coatings, and optoelectronics. Liquid-like mobile ions are effective at disrupting phonon propagation, hence suppressing thermal conduction. However, high ionic mobility leads to the degradation of liquid-like thermoelectric materials under operating conditions due to ion migration and metal deposition at the cathode, hindering their practical application. Here, a new type of behavior, incipient ionic conduction, which leads to ultralow thermal conductivity, while overcoming the issues of degradation inherent in liquid-like materials, is identified. Using neutron spectroscopy and molecular dynamics (MD) simulations, it is demonstrated that in tetrahedrite, an established thermoelectric material with a remarkably low thermal conductivity, copper ions, although mobile above 200 K, are predominantly confined to cages within the crystal structure. Hence the undesirable migration of cations to the cathode can be avoided. These findings unveil a new approach for the design of materials with ultralow thermal conductivity, by exploring systems in which incipient ionic conduction may be present.

Lone Pair Rotation and Bond Heterogeneity Leading to Ultralow Thermal Conductivity in Aikinite.

Understanding the relationship between the crystal structure, chemical bonding, and lattice dynamics is crucial for the design of materials with low thermal conductivities, which are essential in fields as diverse as thermoelectrics, thermal barrier coatings, and optoelectronics. The bismuthinite-aikinite series, Cu1-x□xPb1-xBi1+xS3 (0 ≤ x ≤ 1, where □ represents a vacancy), has recently emerged as a family of n-type semiconductors with exceptionally low lattice thermal conductivities. We present a detailed investigation of the structure, electronic properties, and the vibrational spectrum of aikinite, CuPbBiS3 (x = 0), in order to elucidate the origin of its ultralow thermal conductivity (0.48 W m-1 K-1 at 573 K), which is close to the calculated minimum for amorphous and disordered materials, despite its polycrystalline nature. Inelastic neutron scattering data reveal an anharmonic optical phonon mode at ca. 30 cm-1, attributed mainly to the motion of Pb2+ cations. Analysis of neutron diffraction data, together with ab-initio molecular dynamics simulations, shows that the Pb2+ lone pairs are rotating and that, with increasing temperature, Cu+ and Pb2+ cations, which are separated at distances of ca. 3.3 Å, exhibit significantly larger displacements from their equilibrium positions than Bi3+ cations. In addition to bond heterogeneity, a temperature-dependent interaction between Cu+ and the rotating Pb2+ lone pair is a key contributor to the scattering effects that lower the thermal conductivity in aikinite. This work demonstrates that coupling of rotating lone pairs and the vibrational motion is an effective mechanism to achieve ultralow thermal conductivity in crystalline materials.

Tin-Substituted Chalcopyrite: An n-Type Sulfide with Enhanced Thermoelectric Performance.

The dearth of n-type sulfides with thermoelectric performance comparable to that of their p-type analogues presents a problem in the fabrication of all-sulfide devices. Chalcopyrite (CuFeS2) offers a rare example of an n-type sulfide. Chemical substitution has been used to enhance the thermoelectric performance of chalcopyrite through preparation of Cu1-x Sn x FeS2 (0 ≤ x ≤ 0.1). Substitution induces a high level of mass and strain field fluctuation, leading to lattice softening and enhanced point-defect scattering. Together with dislocations and twinning identified by transmission electron microscopy, this provides a mechanism for scattering phonons with a wide range of mean free paths. Substituted materials retain a large density-of-states effective mass and, hence, a high Seebeck coefficient. Combined with a high charge-carrier mobility and, thus, high electrical conductivity, a 3-fold improvement in power factor is achieved. Density functional theory (DFT) calculations reveal that substitution leads to the creation of small polarons, involving localized Fe2+ states, as confirmed by X-ray photoelectron spectroscopy. Small polaron formation limits the increase in carrier concentration to values that are lower than expected on electron-counting grounds. An improved power factor, coupled with substantial reductions (up to 40%) in lattice thermal conductivity, increases the maximum figure-of-merit by 300%, to zT ≈ 0.3 at 673 K for Cu0.96Sn0.04FeS2.

A Tunable Structural Family with Ultralow Thermal Conductivity: Copper-Deficient Cu1-x□xPb1-xBi1+xS3.

Understanding the mechanism that connects heat transport with crystal structures and order/disorder phenomena is crucial to develop materials with ultralow thermal conductivity (κ), for thermoelectric and thermal barrier applications, and requires the study of highly pure materials. We synthesized the n-type sulfide CuPbBi5S9 with an ultralow κ value of 0.6-0.4 W m-1 K-1 in the temperature range 300-700 K. In contrast to prior studies, we show that this synthetic sulfide does not exhibit the ordered gladite mineral structure but instead forms a copper-deficient disordered aikinite structure with partial Pb replacement by Bi, according to the chemical formula Cu1/3□2/3Pb1/3Bi5/3S3. By combining experiments and lattice dynamics calculations, we elucidated that the ultralow κ value of this compound is due to very low energy optical modes associated with Pb and Bi ions and, to a smaller extent, Cu. This vibrational complexity at low energy hints at substantial anharmonic effects that contribute to enhance phonon scattering. Importantly, we show that this aikinite-type sulfide, despite being a poor semiconductor, is a potential matrix for designing novel, efficient n-type thermoelectric compounds with ultralow κ values. A drastic improvement in the carrier concentration and thermoelectric figure of merit have been obtained upon Cl for S and Bi for Pb substitution. The Cu1-x□xPb1-xBi1+xS3 series provides a new, interesting structural prototype for engineering n-type thermoelectric sulfides by controlling disorder and optimizing doping.

Crystal structure of (C9H17N2)3[Bi2I9].

Single crystals of tris-(2,3,4,6,7,8,9,10-octa-hydro-pyrimido[1,2-a]azepin-1-ium) tri-µ2-iodido-bis-[tri-iodido-bis-muth(III)], (C9H17N2)3[Bi2I9], were prepared by a solvothermal method, heating a mixture of BiI3, KI, 1,8-di-aza-bicyclo-[5.4.0]undec-7-ene (DBU) and ethanol at 443 K for six days. The asymmetric unit of the title compound, which crystallizes in the monoclinic space group P21/c, contains one [Bi2I9]3- anion and three protonated DBUH+ moieties. The dinuclear [Bi2I9]3- anions, which are composed of face-sharing BiI6 3- octa-hedra, are packed in columns parallel to the [010] direction, and separated by protonated DBUH+ moieties. The optical band gap of (C9H7N2)3Bi2I9 is 2.1 eV.

A Discrete Ligand-Free T3 Supertetrahedral Cluster of Gallium Sulfide.

Large discrete supertetrahedral clusters of metal chalcogenides are rare due to the difficulty of crystallizing solids in which the negative charge of the cluster is balanced by the positive charges of the countercations. Here, we describe a discrete ligand-free T3 supertetrahedral cluster, [Ga10S16(SH)4]6-, which was successfully synthesized in the presence of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) using the neutral surfactant polyethyleneglycol (PEG)-400 as the reaction solvent. Protonated DBUH+ cations are incorporated into the crystal structure of the product, which can be formulated as [C9H17N2]6[Ga10S16(SH)4]. This compound, which represents the first example of a discrete ligand-free T3 cluster of gallium sulfide, was fully characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and ultraviolet-visible diffuse reflectance. The results presented here indicate that the use of surfactants as solvents offers potential for the preparation of new compounds containing supertetrahedral clusters.

Insights into the Mechanochemical Synthesis of MOF-74.

Mechanochemical synthesis has recently emerged as a scalable "green" approach for the preparation of MOFs, but current understanding of the underlying reaction mechanisms is limited. In this work, an investigation of the reaction pathway of the mechanochemical synthesis of MOF-74 from ZnO and 2,5-dihydroxyterephthalic acid (H4HDTA), using DMF as a liquid additive, is presented. The complex reaction pathway involves the formation of four short-lived intermediate phases, prior to the crystallization of MOF-74. The crystal structures of three of these intermediates have been determined using a combination of single-crystal and powder X-ray diffraction methods and are described here. The initial stages of the reaction are very fast, with a DMF solvate of H4HDTA forming after only 2 min of milling. This is followed by crystallization, after only 4 min of milling, of a triclinic one-dimensional coordination polymer, Zn(H2DHTA)(DMF)2(H2O)2, which converts into a monoclinic polymorph on additional milling. Highly crystalline MOF-74 appears after prolonged milling, for at least 70 min.

Multiple Roles of 1,4-Diazabicyclo[2.2.2]octane in the Solvothermal Synthesis of Iodobismuthates.

Hybrid bismuth-containing halides are emerging as alternative candidates to lead-containing perovskites for light-harvesting applications, as Bi3+ is isoelectronic with Pb2+ and the presence of an active lone pair of electrons is expected to result in outstanding charge-carrier transport properties. Here, we report a family of one binary and three ternary iodobismuthates containing 1,4-diazabicyclo[2.2.2]octane (DABCO). These materials have been prepared solvothermally and their crystal structures, thermal stability, and optical properties determined. Reactions carried out in the presence of bismuth iodide and DABCO produced (C6H12N2)BiI3 (1), which consists of hybrid ribbons in which pairs of edge-sharing bismuth octahedra are linked by DABCO ligands. Short I···I contacts give rise to a three-dimensional network. Similar reactions in the presence of copper iodide produced (C8H17N2)2Bi2Cu2I10 (2) and [(C6H13N2)2BiCu2I7](C2H5OH) (3) in which either ethylated DABCO cations (EtDABCO)+ or monoprotonated DABCO cations (DABCOH)+ are coordinated to copper in discrete tetranuclear and trinuclear clusters, respectively. In the presence of potassium iodide, a unique three-dimensional framework, (C6H14N2)[(C6H12N2)KBiI6] (4), was formed, which contains one-dimensional hexagonal channels approximately 6 Å in diameter. The optical band gaps of these materials, which are semiconductors, range between 1.82 and 2.27 eV, with the lowest values found for the copper-containing discrete clusters. Preliminary results on the preparation of thin films are presented.

Improved Thermoelectric Performance through Double Substitution in Shandite-Type Mixed-Metal Sulfides.

Substitution of tin by indium in shandite-type phases, A3Sn2S2 with mixed Co/Fe occupancy of the A-sites is used to tune the Fermi level within a region of the density of states in which there are sharp, narrow bands of predominantly metal d-character. Materials of general formula Co2.5+x Fe0.5-x Sn2--yIn y S2 (x = 0, 0.167; 0.0 ≤ y ≤ 0.7) have been prepared by solid-state reaction and the products characterized by powder X-ray diffraction. Electrical-transport property data reveal that the progressive depopulation of the upper conduction band as tin is replaced by indium increases the electrical resistivity, and the weakly temperature-dependent ρ(T) becomes more semiconducting in character. Concomitant changes in the negative Seebeck coefficient, the temperature dependence of which becomes increasingly linear, suggests the more highly substituted materials are n-type degenerate semiconductors. The power factors of the substituted phases, while increased, exhibit a weak temperature dependence. The observed reductions in thermal conductivity are principally due to reductions in the charge-carrier contribution on hole doping. A maximum figure-of-merit of (ZT)max = 0.29 is obtained for the composition Co2.667Fe0.333Sn1.6In0.4S2 at 573 K: among the highest values for an n-type sulfide at this temperature.

Understanding the origin of disorder in kesterite-type chalcogenides A2ZnBQ4 (A = Cu, Ag; B = Sn, Ge; Q = S, Se): the influence of inter-layer interactions.

Semiconducting quaternary chalcogenides with A2ZnBQ4 stoichiometry, where A and B are monovalent and tetravalent metal ions and Q is a chalcogen (e.g. Cu2ZnSnS4 or CZTS) have recently attracted attention as potential solar-cell absorbers made from abundant and non-toxic elements. Unfortunately, they exhibit relatively poor sunlight conversion efficiencies, which has been linked to site disorder within the tetrahedral cation sub-lattice. In order to gain a better understanding of the factors controlling cation disorder in these chalcogenides, we have used powder neutron diffraction, coupled with Density Functional Theory (DFT) simulations, to investigate the detailed structure of A2ZnBQ4 phases, with A = Cu, Ag; B = Sn, Ge; and Q = S, Se. Both DFT calculations and powder neutron diffraction data demonstrate that the kesterite structure (space group: I4[combining macron]) is adopted in preference to the higher-energy stannite structure (space group: I4[combining macron]2m). The contrast between the constituent cations afforded by neutron diffraction reveals that copper and zinc cations are only partially ordered in the kesterites Cu2ZnBQ4 (B = Sn, Ge), whereas the silver-containing phases are fully ordered. The degree of cation order in the copper-containing phases shows a greater sensitivity to the identity of the B-cation than to the chalcogenide anion. DFT indicates that cation ordering minimises inter-planar Zn2+Zn2+ electrostatic interactions, while there is an additional intra-planar energy contribution associated with size mismatch. The complete Ag/Zn order in Ag2ZnBQ4 (B = Sn, Ge) phases can thus be related to the anisotropic expansion of the unit cell on replacing Cu with Ag.