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Solid solutions of Yb2-xAxCdSb2 (A = Ca, Sr, Eu; x ≤ 1) are of interest for their promising thermoelectric (TE) properties. Of these solid solutions, Yb2-xCaxCdSb2 has end members with different crystal structures. Yb2CdSb2 crystallizes in the polar space group Cmc21, whereas Ca2CdSb2 crystallizes in the centrosymmetric space group Pnma. Other solid solutions, Yb2-xAxCdSb2 (A = Sr, Eu), crystallize in the polar space group for x ≤ 1, and compositions with x ≥ 1 have not been reported. Both structure types are composed of corner-sharing CdSb4 tetrahedra condensed into sheets that differ by the stacking of the layers. Single crystals of the solid solution Yb2-xCaxCdSb2 (x = 0-1) were studied to elucidate the structural transition between the Yb2CdSb2 and Ca2CdSb2 structure types. For x ≤ 1, the structures remain in the polar space group Cmc21. As the Ca content is increased, a positional disorder arises in the intralayer cation sites (Yb2/Ca2) and the Cd site, resulting in inversion of the CdSb4 tetrahedral chain. This phenomenon could be indicative of an intergrowth of the opposing space group. The TE properties of polycrystalline samples of Yb2-xCaxCdSb2 (x ≤ 1) were measured from 300 to 525 K. The lattice thermal conductivity is extremely low (0.3-0.4 W/m·K) and the Seebeck coefficients are high (100-180 μV/K) across the temperature range. First-principles calculations show a minimum in the thermal conductivity for the x = 0.3 composition, in good agreement with experimental data. The low thermal conductivity stems from the acoustic branches being confined to low frequencies and a large number of phonon scattering channels provided by the localized optical branches. The TE quality factor of the Yb1.7A0.3CdSb2 (A = Ca, Sr, Eu) series has been calculated and predicts that the A = Ca and Sr solid solutions may not improve with carrier concentration optimization but that the Eu series is worthy of additional modifications. Overall, the x = 0.3 compositions provide the highest zT because they provide the best electronic properties with the lowest thermal conductivity.

With the emergence of graphene, the first two-dimensional (2D) material, many other 2D materials have been discovered and examined for novel applications. Various synthesis approaches have been emp...

The structure, magnetic properties, and 151Eu and 119Sn Mossbauer spectra of the solid-solution Eu11–xSrxZn4Sn2As12 are presented. A new commensurately modulated structure is described for Eu11Zn4S...

The rapid rise of atmospheric CO2 has spurred keen research interest in sustainable energy technologies including thermoelectric materials which can reliably and robustly turn heat directly to elec...

Microwave-assisted heating methods have been used to synthesize oleylamine-capped Ge1–xSnx nanocrystals. By varying the reaction temperature while keeping the Ge and Sn precursor concentrations con...

Yb14MnSb11 is a p-type high-temperature thermoelectric material with operational temperatures as high as 1273 K. Rare-earth (RE) substitution into this phase has been shown to increase the melting ...

The mineral Zlatogorite, CuNiSb2, was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb2-AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb2-AP crystallizes in the NiAs-derived structure (P3m1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb6 and CuSb6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure (P63/mmc, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb2-AP. The magnetic measurement indicates that CuNiSb2-AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb2-AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb2-8 GPa) was prepared by pressing CuNiSb2-AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb2-8 GPa are best fit with a disordered metal structure in the P3m1 space group, corroborated by transmission electron microscopy.

We report a systematic study on the synthesis of highly monodisperse hollow Ge nanoparticles via galvanic replacement reactions between GeI2 and Ag NPs. By fine-tuning the synthetic parameters such...

The numerous electronic and optoelectronic applications that rely on semiconductors require tuning their properties through doping. Germanium quantum dots (Ge QDs) were successfully doped with bism...

Indirect ligand exchange methods have been demonstrated to replace the oleylamine capping with dodecanethiol for germanium nanocrystals (Ge NCs). In these methods, hydrazine is employed to effectiv...

Composite phases have been shown to improve both the thermoelectric efficiency and mechanical properties of materials. Here, we demonstrate an improved thermoelectric figure of merit, power factor,...

Thermoelectric materials are a unique class of compounds that can recycle energy through conversion of heat into electrical energy. A new 21–4–18 Zintl phase has been discovered in the Yb–Mn–Sb sys...

The reduction of Ge halides in oleylamine (OAm) provides a simple, yet effective high-yield synthetic route to germanium nanocrystals (NCs). Significant advances based on this approach include size...

Topological insulators (TIs) are a class of materials that can exhibit robust spin polarizations at the surfaces and have attracted much attention toward spintronic applications. Here, we optimized...

Type I clathrates of the composition K8E8Ge38 (E = Al, Ga, In) were prepared via the reaction of KH with E and Ge and thermoelectric properties measured in order to compare to K8Al8Si38, a promisin...

BaFe2As2 superconductors doped with Co or Ni were synthesized by heat treatment of the reactive BaH2 precursor and elemental Fe, Co, Ni, and As in a sealed niobium container. The hydride route prov...

We report the synthesis, structure, and magnetic properties of a new Zintl phase and structure type, Eu11Zn4Sn2As12. The structure and composition of this phase have been established by single-crystal X-ray diffraction and electron microprobe analysis. Eu11Zn4Sn2As12 crystallizes in monoclinic space group C2/c (No. 15) with the following lattice parameters: a = 7.5679(4) A, b = 13.0883(6) A, c = 31.305(2) A, and β = 94.8444(7)° [R1 = 0.0398; wR2 = 0.0633 (all data)]. The anisotropic structural features staggered ethane-like [Sn2As6]12– units and infinite ∞2[Zn2As3]5– sheets extended in the a–b plane. Eu cations fill the space between these anionic motifs. Temperature-dependent magnetic properties and magnetoresistance of this Zintl phase have been studied, and the electronic structure and chemical bonding were elucidated using first-principles quantum chemical calculations (TB-LMTO-ASA). Quantum chemical calculations show that the ethane-like units can be considered as consisting of covalent single bonds;...

Polycrystalline samples of CoAsSb were prepared by annealing a stoichiometric mixture of the elements at 1073 K for 2 weeks. Synchrotron powder X-ray diffraction refinement indicated that CoAsSb adopts arsenopyrite-type structure with space group P21/c. Sb vacancies were observed by both elemental and structural analysis, which indicate CoAsSb0.883 composition. CoAsSb was thermally stable up to 1073 K without structure change but decomposed at 1168 K. Thermoelectric properties were measured from 300 to 1000 K on a dense pellet. Electrical resistivity measurements revealed that CoAsSb is a narrow-band-gap semiconductor. The negative Seebeck coefficient indicated that CoAsSb is an n-type semiconductor, with the maximum value of −132 μV/K at 450 K. The overall thermal conductivity is between 2.9 and 6.0 W/(m K) in the temperature range 300–1000 K, and the maximum value of figure of merit, zT, reaches 0.13 at 750 K. First-principles calculations of the electrical resistivity and Seebeck coefficient confirmed ...

Solvent effects on the microwave-assisted synthesis of germanium nanoparticles are presented. A mixture of oleylamine and 1-dodecene was used as the reaction solvent. Oleylamine serves as a reducing agent in the synthesis while both molecules act as binding ligands. Increased concentrations of 1-dodecene in the solvent mixture were found to increase the size of the formed nanoparticles. Crystallinity was also dependent on the solvent mixture. Amorphous nanoparticles were obtained at lower 1-dodecene concentrations, whereas, at higher concentrations, particles contained crystalline and amorphous domains. 11-Methoxyundec-1-ene was synthesized to replace 1-dodecene in the reaction mixture for nuclear magnetic resonance (NMR) studies. 1H NMR of the reaction products shows that both solvent molecules in the system act as binding ligands on the nanoparticle surface. Nanoparticles were characterized using powder X-ray diffraction, scanning transmission electron microscopy, and spectroscopy techniques (Raman, UV–...

Zintl phases are promising thermoelectric materials because they are composed of both ionic and covalent bonding, which can be independently tuned. An efficient thermoelectric material would have regions of the structure composed of a high-mobility compound semiconductor that provides the “electron–crystal” electronic structure, interwoven (on the atomic scale) with a phonon transport inhibiting structure to act as the “phonon–glass”. The phonon–glass region would benefit from disorder and therefore would be ideal to house dopants without disrupting the electron–crystal region. The solid solution of the Zintl phase, Yb2–xEuxCdSb2, presents such an optimal structure, and here we characterize its thermoelectric properties above room temperature. Thermoelectric property measurements from 348 to 523 K show high Seebeck values (maximum of ∼269 μV/K at 523 K) with exceptionally low thermal conductivity (minimum ∼0.26 W/m K at 473 K) measured via laser flash analysis. Speed of sound data provide additional suppo...

Nanogermanium is a material that has great potential for technological applications, and doped and alloyed Ge nanocrystals (NCs) are actively being considered. New alloys and compositions are possible in colloidal synthesis because the reactions are kinetically rather than thermodynamically controlled. Most of the Group V elements have been shown to be n-type dopants in Ge to increase carrier concentration; however, thermodynamically, Bi shows no solubility in crystalline Ge. Bi-doped Ge NCs were synthesized for the first time in a microwave-assisted solution route. The oleylamine capping ligand can be replaced by dodecanethiol without loss of Bi. A positive correlation between the lattice parameter and the concentration of Bi content (0.5–2.0 mol %) is shown via powder X-ray diffraction and selected area electron diffraction. X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), scanning TEM, and inductively coupled plasma–mass spectroscopy are consistent with the Bi solubility up to ...

Water-soluble poly(allylamine) Mn2+-doped Si (SiMn) nanoparticles (NPs) were prepared and show promise for biologically related applications. The nanoparticles show both strong photoluminescence and good magnetic resonance contrast imaging. The morphology and average diameter were obtained through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM); spherical crystalline Si NPs with an average diameter of 4.2 ± 0.7 nm were observed. The doping maximum obtained through this process was an average concentration of 0.4 ± 0.3% Mn per mole of Si. The water-soluble SiMn NPs showed a strong photoluminescence with a quantum yield up to 13%. The SiMn NPs had significant T1 contrast with an r1 relaxivity of 11.1 ± 1.5 mM-1 s-1 and r2 relaxivity of 32.7 ± 4.7 mM-1 s-1 where the concentration is in mM of Mn2+. Dextran-coated poly(allylamine) SiMn NPs produced NPs with T1 and T2 contrast with a r1 relaxivity of 27.1 ± 2.8 mM-1 s-1 and r2 relaxivity of 1078.5 ± 1.9 mM-1 s-1. X-band electron paramagnetic resonance spectra are fit with a two-site model demonstrating that there are two types of Mn2+ in these NP's. The fits yield hyperfine splittings (A) of 265 and 238 MHz with significant zero field splitting (D and E terms). This is consistent with Mn in sites of symmetry lower than tetrahedral due to the small size of the NP's.

Eu11–xYbxCd6Sb12 Zintl solid solutions have been prepared by tin flux reaction by employing the elements Eu/Yb/Cd/Sb/Sn in the ratio 11 – xp:xp:6:12:30, where xp is an integer less than 11 representing the preparative amount of Eu (11 – xp) and Yb (xp). Efforts to make the Yb compositions for x exceeding ∼3 resulted in structures other than the Sr11Cd6Sb12 structure type. The crystal structures and compositions were determined by single-crystal and powder X-ray diffraction and wavelength-dispersive X-ray analysis measurements. The title solid-solution Zintl compounds crystallize in the centrosymmetric monoclinic space group C2/m (no. 12, Z = 2) as the Sr11Cd6Sb12 structure type (Pearson symbol mC58), and the lattice parameters decrease with increasing ytterbium content. Single crystal X-ray diffraction shows that Yb atoms are not randomly distributed in the Eu sites but have a site preference which can be attributed to size effects. The influence of the rare earth (RE) metal sites on thermal and electroni...

The thermal stability and thermoelectric properties of type I clathrate K8Al8Si38 up to 873 K are reported. K8Al8Si38 possesses a high absolute Seebeck coefficient value and high electrical resistivity in the temperature range of 323 to 873 K, which is consistent with previously reported low temperature thermoelectric properties. Samples with Ba partial substitution at the K guest atom sites were synthesized from metal hydride precursors. The samples with the nominal chemical formula of K8–xBaxAl8+xSi38–x (x = 1, 1.5, 2) possess type I clathrate structure (cubic, Pm3n), confirmed by X-ray diffraction. The guest atom site occupancies and thermal motions were investigated with Rietveld refinement of synchrotron powder X-ray diffraction. Transport properties of Ba-containing samples were characterized from 2 to 300 K. The K–Ba alloy phases showed low thermal conductivity and improved electrical conductivity compared to K8Al8Si38. Electrical resistivity and Seebeck coefficients were measured over the tempera...

A novel Zintl phase structure type, Eu7Cd4Sb8-xAsx (x = 2, 3, 4, and 5), with the general formula Eu7Cd4Pn8 (Pn = mixed occupancy Sb and As), was synthesized by molten tin flux reaction. Its structure was determined using single-crystal X-ray diffraction methods. This structure type is only preserved for 2 ≤ x ≤ 5 under our experimental conditions, and efforts to synthesize samples with x2 or x5 resulted in other structure types. The mixed occupancy Sb and As can be thought of as a pseudoatom whose ideal size, in this range of Sb/As ratios, fits the structure. The title phase crystallizes in the I-centered monoclinic space group I2/m (No. 12, Z = 4) with unit cell parameters ranging as follows: a = 19.7116(17)-19.4546(13) Å, b = 4.6751(4)-4.6149(3) Å, c = 24.157(2)-23.871(15) Å, and β = 95.8798(1)-96.016(5)°, depending on the Sb/As ratio. The structure can be described as parallel double pentagonal tubes resulting from Cd-Pn and Pn-Pn bonding. These double pentagons are formed through corner sharing of the Cd-centered CdPn4 tetrahedra and a Pn-Pn interaction from two adjacent CdPn4 tetrahedra. This structure type is closely related to the Sr11Cd6Sb12 structure type as both share the same bonding features of Pn-Pn bonding and double pentagonal tubes. Electron microprobe analysis confirms the composition of these new Zintl solid solution phases. The As exhibits preferential substitution on specific sites, and site specificity trends are supported by lowest energy models from theoretical calculations. Theoretical calculations also predict that Sb-rich compounds should be metallic or semimetallic and that they should become more insulating as As content increases. Members of the solid-solution order ferromagnetically between 5 and 6 K and exhibit relatively low electrical resistivity between 50 and 300 K, ranging from ∼0.57 to ∼26 mΩ·cm, increasing with increasing As content.

The synthesis and transport properties of the family of coinage metal-stuffed Zintl compounds, Eu9Cd4–xCM2+x–y□ySb9 (CM = coinage metal, □ = vacancies), is presented as a function of coinage metal substitution. Eu9Cd4–xCM2+x–y□ySb9 compounds are shown to be rare examples of metallic Zintl phases with low thermal conductivities. While the lattice thermal conductivity is low, which is attributed to the complex structure and presence of interstitials, the electronic contribution to thermal conductivity is also low. In these p-type compounds, the carriers transmit less heat than expected, based on the Wiedemann–Franz law and metallic conduction, κe = L0T/ρ. Density functional theory (DFT) calculations indicate that the Fermi level resides in a pseudo-gap, which is consistent with the metallic description of the properties. While the contribution from the interstitial CM states to the Fermi level is small, the interstitial CMs are required to tune the position of the Fermi level. Analysis of the topology of el...

Compounds of the Yb14MnSb11 structure type are the highest efficiency bulk p-type materials for high temperature thermoelectric applications, with reported figures of merit (ZTs) as high as ∼1.3 at 1275 K. Further optimization of ZT for this structure type is possible with the development of a simple synthetic route. However, this has been difficult to achieve because of the small amount of Mn required compared with Yb and Sb. A simple synthetic route for Yb14MnSb11 has been developed utilizing a combination of ball milling and annealing to produce phase-pure material followed by spark plasma sintering for consolidation. The materials have been characterized by powder X-ray diffraction before and after spark plasma sintering. The stoichiometric reaction of Yb, Sb, and MnSb provides phase-pure powder by X-ray diffraction. Upon cycling to temperatures greater than 1272 K, Yb14MnSb11 shows the presence of Yb11Sb10. Additional samples with 5% and 10% excess Mn were also investigated. Adding 5–10% excess Mn do...

Solid-solution Zintl compounds with the formula Eu11Cd6–xZnxSb12 have been synthesized from the elements as single crystals using a tin flux according to the stoichiometry Eu:Cd:Zn:Sb:Sn of 11:6–xp:xp:12:30 with xp = 0, 1, 2, 3, 4, 5, and 6, where xp is the preparative amount of Zn employed in the reaction. The crystal structures and the compositions were established by single-crystal as well as powder X-ray diffraction and wavelength-dispersive X-ray analysis measurements. The title solid-solution Zintl compounds crystallize isostructurally in the centrosymmetric monoclinic space group C 2/m (No. 12, Z = 2) as the Sr11Cd6Sb12 structure type (Pearson symbol mC58). There is a miscibility gap at 3 ≤ xp ≤ 4 where the major product crystallizes in a disordered structure related to the Ca9Mn4Bi9 structure type; otherwise, for all other compositions, the Sr11Cd6Sb12 structure is the majority phase. Eu11Cd6Sb12 shows lower lattice thermal conductivity relative to Eu11Zn6Sb12 consistent with its higher mean atomi...

A series of alkali metal containing compounds with type I clathrate structure, A8Ga8Si38 (A = K, Rb, Cs) and K8Al8Si38, were synthesized and characterized. Room temperature lattice parameters of A8Ga8Si38 (A = K, Rb, Cs) and K8Al8Si38 were determined to be 10.424916(10), 10.470174(13), 10.535069(15), and 10.48071(2) A, respectively. The type I clathrate structure (cubic, Pm3n) was confirmed for all phases, and in the case of K8Al8Si38 and K8Ga8Si38, the structures were also refined using synchrotron powder diffraction data. The samples were consolidated by Spark Plasma Sintering (SPS) for thermoelectric property characterization. Electrical resistivity was measured by four probe AC transport method in the temperature range of 30 to 300 K. Seebeck measurements from 2 to 300 K were consistent with K8Al8Si38 and K8Ga8Si38 being n-type semiconductors, while Rb8Ga8Si38 and Cs8Ga8Si38 were p-type semiconductors. K8Al8Si38 shows the lowest electrical resistivity and the highest Seebeck coefficient. This phase a...

Inorganic semiconductor nanoparticles are of significant interest for applications that benefit from their size-dependent properties. The work presented here focuses on the characterization of solution-based microwave synthesized Ge nanocrystals (NCs). Three differently capped Ge NCs were investigated: oleylamine (OAM), dodecanethiol (DDT), and a functionalized N4,N4,N4′,N4′-tetraphenylbiphenyl-4,4′-diamine (TPD) ligand, which is commonly used as hole-transporting units. The optical gaps followed the expected trend for quantum confinement; however, the absolute value depended upon the ligand. We found that the DDT-capped Ge NCs feature consistently larger bandgaps than OAM-capped Ge NCs of a similar size. Cyclic voltammetry (CV) was used to determine the valence band energy for OAM-capped Ge NCs, and the conduction band energy was estimated from the optical gap. By contrast, DDT-capped Ge NCs and the OAM/DDT-capped Ge NCs did not exhibit an oxidative signal in the cyclic voltammetry. This was attributed t...

Magnesium-containing Zintl phase compounds Yb14MgSb11 and Ca14MgSb11 have been prepared by annealing the mixture of the elements at 1075–1275 K. These compounds are isostructural with the Zintl compound Ca14AlSb11 and crystallize in the tetragonal space group I41/acd (Z = 8). Single-crystal X-ray data (90 K) were refined for Yb14MgSb11 [a = 16.625(9) A, c = 22.24(2) A, V = 6145(8) A3, and R1/wR2 (0.0194/0.0398)] and Ca14MgSb11 [a = 16.693(2) A, c = 22.577(5) A, V = 6291(2) A3, R1/wR2 (0.0394/0.0907)]. This structure type has been shown to be highly versatile with a large number of phases with the general formula A14MPn11 (A = Ca, Sr, Ba, Yb, Eu; M = Mn, Zn, Nb, Cd, Group 13 elements; Pn = Group 15 elements). The two compounds reported in this paper are the first Mg-containing analogs. Replacing M with Mg, which is divalent with no d-orbitals, probes electronic structure and properties of this structure type. Mg2+ is well-known to prefer tetrahedral geometry and allows for integration of the properties of ...

We have developed a fast, easy, and scalable synthesis method for Ba1xKxFe2As2 (0 ≤ x ≤ 1) superconductors using hydrides BaH2 and KH as a source of barium and potassium metals. Synthesis from hydrides provides better mixing and easier handling of the starting materials, consequently leading to faster reactions and/or lower synthesis temperatures. The reducing atmosphere provided by the evolved hydrogen facilitates preparation of oxygen-free powders. By a combination of methods we have shown that Ba1xKxFe2As2 obtained via hydride route has the same characteristics as when it is prepared by traditional solid-state synthesis. Refinement from synchrotron powder X-ray diffraction data confirms a linear dependence of unit cell parameters upon K content as well as the tetragonal to orthorhombic transition at low temperatures for compositions with x < 0.2. Magnetic measurements revealed dome-like dependence of superconducting transition temperature Tc upon K content with a maximum of 38 K for x close to 0.4. Electron diffraction and high-resolution high-angle annular dark-field scanning transmission electron microscopy indicates an absence of Ba/K ordering, while local inhomogeneity in the Ba/K distribution takes place at a scale of several angstroms along [110] crystallographic direction.

The synthesis, crystal structure, magnetic properties, and europium Mossbauer spectroscopy of the new members of the 9–4–9 Zintl family of Eu9Cd4–xCM2+x–y□ySb9 (CM = coinage metal: Au, Ag, and Cu) are reported. These compounds crystallize in the Ca9Mn4Bi9 structure type (9–4–9) with the 4g interstitial site almost half-occupied by coinage metals; these are the first members in the 9–4–9 family where the interstitial positions are occupied by a monovalent metal. All previously known compounds with this structure type include divalent interstitials where these interstitials are typically the same as the transition metals in the anionic framework. Single-crystal magnetic susceptibility data indicate paramagnetic behavior for all three compounds with antiferromagnetic ordering below 10 K (at 100 Oe) that shifts to lower temperature (

A thermochemical study of three germanium allotropes by differential scanning calorimetry (DSC) and oxidative high-temperature drop solution calorimetry with sodium molybdate as the solvent is described. Two allotropes, microcrystalline allo-Ge (m-allo-Ge) and 4H-Ge, have been prepared by topotactic deintercalation of Li_7Ge_(12) with methanol (m-allo-Ge) and subsequent annealing at 250 °C (4H-Ge). Transition enthalpies determined by differential scanning calorimetry amount to 4.96(5) ± 0.59 kJ/mol (m-allo-Ge) and 1.46 ± 0.55 kJ/mol (4H-Ge). From high-temperature drop solution calorimetry, they are energetically less stable by 2.71 ± 2.79 kJ/mol (m-allo-Ge) and 5.76 ± 5.12 kJ/mol (4H-Ge) than α-Ge, which is the stable form of germanium under ambient conditions. These data are in agreement with DSC, as well as with the previous quantum chemical calculations. The morphology of the m-allo-Ge and 4H-Ge crystallites was investigated by a combination of scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. Even though the crystal structures of m-allo-Ge and 4H-Ge cannot be considered as truly layered, these phases retain the crystalline morphology of the layered precursor Li_7Ge_(12). Investigation by diffuse reflectance infrared Fourier transform spectroscopy and UV–vis diffuse reflectance measurements reveal band gaps in agreement with quantum chemical calculations.

Applications of Ge nanocrystals (NCs) are limited by the stability and air reactivity of the Ge surface. In order to promote stability and increase the diversity of ligand functionalization of Ge NCs, the preparation of thiol-passivated Ge NCs via a ligand exchange process was investigated. Herein a successful replacement of oleylamine ligands on the surface of Ge NCs with dodecanethiol is reported. The successful ligand exchange was monitored by FTIR and NMR spectroscopy and it was found that dodecanethiol provided a better surface coverage, leading to stable Ge NC dispersions. Dodecanethiol capping also enabled band gap determination of the NCs by surface photovoltage (SPV) spectroscopy. The SPV measurements indicated an efficient charge separation in the ligand-exchanged Ge NCs. On the other hand, oleylamine-terminated Ge NCs of similar sizes exhibited a very small photovoltage, indicating a poorly passivated surface.

Zintl phases are compounds that have shown promise for thermoelectric applications. The title solid–solution Zintl compounds were prepared from the elements as single crystals using a tin flux for compositions x = 0, 1, 2, and 3. Eu_(11)Cd_6Sb_(12–x)As_x (x < 3) crystallize isostructurally in the centrosymmetric monoclinic space group C2/m (no. 12, Z = 2) as the Sr_(11)Cd_6Sb_(12) structure type (Pearson symbol mC58). Efforts to make the As compositions for x exceeding ~3 resulted in structures other than the Sr_(11)Cd_6Sb_(12) structure type. Single-crystal X-ray diffraction indicates that As does not randomly substitute for Sb in the structure but is site specific for each composition. The amount of As determined by structural refinement was verified by electron microprobe analysis. Electronic structures and energies calculated for various model structures of Eu_(11)Cd_6Sb_(10)As_2 (x = 2) indicated that the preferred As substitution pattern involves a mixture of three of the six pnicogen sites in the asymmetric unit. In addition, As substitution at the Pn4 site opens an energy gap at the Fermi level, whereas substitution at the other five pnicogen sites remains semimetallic with a pseudo gap. Thermoelectric properties of these compounds were measured on hot-pressed, fully densified pellets. Samples show exceptionally low lattice thermal conductivities from room temperature to 775 K: 0.78–0.49 W/mK for x = 0; 0.72–0.53 W/mK for x = 1; and 0.70–0.56 W/mK for x = 2. Eu_(11)Cd_6Sb_(12) shows a high p-type Seebeck coefficient (from +118 to 153 μ V/K) but also high electrical resistivity (6.8 to 12.8 mΩ·cm). The value of zT reaches 0.23 at 774 K. The properties of Eu_(11)Cd_6Sb_(12–x)As_x are interpreted in discussion with the As site substitution.

A facile size-controlled synthesis (microwave/conventional) of quasi-spherical germanium nanoparticles is reported. Oleylamine serves as a solvent, a binding ligand, and a reducing agent in the synthesis. Reactions were carried out with microwave-assisted heating, and the results have been compared with those produced by conventional heating. Germanium iodides (GeI4, GeI2) were used as the Ge precursor, and size control in the range of 4–11 nm was achieved by controlling the ratio of Ge4+/Ge2+ in the precursor mix. Longer reaction times and higher temperatures were also observed to have an effect on the nanoparticle size distribution. Microwave heating resulted in crystalline nanoparticles at lower temperatures than conventional resistive heating because of the ability of germanium iodides to convert electromagnetic radiation directly to heat. The reported approach for germanium nanoparticle preparation avoids the use of strong reducing agents (LiAlH4, n-BuLi, NaBH4) and HF for etching and, thus, can be c...

The high temperature p-type thermoelectric material Yb(14)MnSb(11) has been of increasing research interest since its high temperature thermoelectric properties were first measured in 2006. Subsequent substitutions of Zn, Al, and La into the structure have shown that this material can be further optimized by altering the carrier concentration or by reduction of spin-disorder scattering. Here the properties of the Yb(14-x)Ca(x)MnSb(11) solid solution series where isovalent Ca(2+) is substituted for Yb(2+) will be presented. Crystals of the Yb(14-x)Ca(x)MnSb(11) solid solution series were made by Sn-flux (x = 2, 4, 6, 8) with the following ratio of elements: (14-x)Yb: xCa: 6 Mn: 11Sb: 86Sn, and their structures determined by single crystal X-ray diffraction. The density of the material significantly decreases by over 2 g/cm(3) as more Ca is added (from x = 1 to 8), because of the lighter mass of Ca. The resulting lower density is beneficial from a device manufacturing perspective where there is often a trade-off with the specific power per kilogram. The compounds crystallize in the Ca(14)AlSb(11) structure type. The Ca substitution contributes to systematic lengthening the Mn-Sb bond while shortening the Sb-Sb bond in the 3 atom linear unit with increasing amounts of Ca. Temperature dependent thermoelectric properties, Seebeck, electrical resistivity, and thermal conductivity were measured from room temperature to 1273 K. Substitution of Yb with Ca improves the Seebeck coefficient while decreasing the thermal conductivity, along with decreasing the carrier concentration in this p-type material resulting in an enhanced thermoelectric figure of merit, zT, compared to Yb(14)MnSb(11).