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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 ...

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...

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 ...

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 ...

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...

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...

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...

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 ...

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...

Chemical hydrides are compounds that can potentially uptake and release hydrogen without the use of hydrogen gas. Nanostructure silicon may have great potential as a chemical hydride. The surface can be capped by hydride and dihydride, and hydrogen can be thermally desorbed from the surface. We have prepared large-scale (1−2 g) samples of hydrogen-capped silicon nanoparticles with average diameters of 60, 10, 5, and 4 nm via a low-temperature chemical method to explore the release of hydrogen from the surface as a function of size. The 60- and 10-nm-diameter particles have only hydrogen on the surface. The 60-nm-diameter particles are crystalline, and the 10-nm-diameter particles are amorphous according to powder X-ray diffraction (XRD). The 5- and 4-nm-diameter particles have both hydrogen and solvent capped on the surface. The 4-nm-diameter particles are amorphous and the 5-nm-diameter particles are crystalline by powder XRD. Weight percentages of ∼3.5% at 350 °C are observed for the 10-nm-diameter part...

Two rare-earth Zintl phases, Yb_(11)GaSb_9 and Yb_(11)InSb_9, were synthesized in high-temperature self-fluxes of molten Ga and In, respectively. Structures were characterized by both single-crystal X-ray diffraction and powder X-ray diffraction and are consistent with the published orthorhombic structure, with the space group Iba2. High-temperature differential scanning calorimetry (DSC) and thermal gravimetry (TG) measurements reveal thermal stability to 1300 K. Seebeck coefficient and resistivity measurements to 1000 K are consistent with the hypothesis that Yb_(11)GaSb_9 and Yb_(11)InSb_9 are small band gap semiconductors or semimetals. Low doping levels lead to bipolar conduction at high temperature, preventing a detailed analysis of the transport properties. Thermal diffusivity measurements yield particularly low lattice thermal conductivity values, less than 0.6 W/m K for both compounds. The low lattice thermal conductivity suggests that Yb_(11)MSb_9 (M = Ga, In) has the potential for high thermoelectric efficiency at high temperature if charge-carrier doping can be controlled.

Single crystals of EuGa2Pn2 (Pn = P, As) were grown from a molten Ga flux and characterized by single-crystal X-ray diffraction at 100(1) K. They are isostructural and crystallize in a new structure type (monoclinic, P2/m, a = 9.2822(9) A, b = 3.8967(4) A, c = 12.0777(11) A, β = 95.5220(10)°, R1 = 0.0148, wR2 = 0.0325 (EuGa2P2) and a = 9.4953(7) A, b = 4.0294(3) A, c = 12.4237(9) A, β = 95.3040(10)°, R1 = 0.0155, wR2 = 0.0315 (EuGa2As2)). The structures consist of alternating layers of two-dimensional Ga2Pn2 anions and Eu cations. The anion layers are composed of Ga2Pn6 staggered, ethane-like moieties having a rare Ga−Ga bonding motif; these moieties are connected in a complex fashion by means of shared Pn atoms. Both structures show small residual electron densities that can be modeled by adding a Eu atom and removing two bonded Ga atoms, resulting in structures (

A series of compounds, Yb_(14)Mn_(1−x)Al_xSb_11 with (0 < x < 1), was prepared via Sn flux and the structures investigated. Single-crystal X-ray diffraction reveals that the volume of the unit cell increases with increasing Al content. Bond-distance changes are less than 2% and the increase in volume of the unit cell is associated with the decreasing distortion of the tetrahedron with increasing Al content. The specific heat, C_p, was measured from 300 to 1100 K. The measured C_p for these compounds is 19% higher than the Dulong-Petit value at the peak zT temperature (1223 K). These measured values permit a recalculation of thermal conductivity, revealing an extremely low lattice thermal conductivity of approximately 0.3−0.4 W/(m K) at 1223 K. The maximum zT of Yb_(14)Mn(1−x)Al_xSb_11 is approximately 0.8 and 1.1 for the x = 0 and x = 0.6 compositions, respectively.

Rare-earth transition metal compounds Yb_(14)Mn_(1−x)Zn_xSb_(11), isostructural with Ca_(14)AlSb_(11), have been prepared using a metal flux growth technique for thermoelectric property measurements (with x = 0.0, 0.2, 0.3, 0.4, 0.7, 0.9, and 1.0). Single-crystal X-ray diffraction and electron microprobe analysis data indicate the successful synthesis of a solid-solution for the Yb_(14)Mn_(1−x)Zn_xSb_(11) structure type for 0 0.4. High-temperature (298 K–1275 K) measurements of the Seebeck coefficient, resistivity, and thermal conductivity were performed on hot-pressed, polycrystalline samples. As the concentration of Zn increases in Yb_(14)Mn_(1−x)Zn_xSb_(11), the Seebeck coefficient remains unchanged for 0 ≤ x ≤ 0.7 indicating that the free carrier concentration has remained unchanged. However, as the nonmagnetic Zn^(2+) ions replace the magnetic Mn^(2+) ions, the spin disorder scattering is reduced, lowering the resistivity. Replacing the magnetic Mn^(2+) with non magnetic Zn^(2+) provides an independent means to lower resistivity without deleterious effects to the Seebeck values or thermal conduction. Alloying the Mn site with Zn reduces the lattice thermal conductivity at low temperatures but has negligible impact at high temperatures. The reduction of spin disorder scattering leads to an ∼10% improvement over Yb_(14)MnSb_(11), revealing a maximum thermoelectric figure of merit (zT) of ∼1.1 at 1275 K for Yb_(14)Mn_(0.6)Zn_(0.4)Sb_(11).

Homogeneous, nanocrystalline La1-xSrxMnO3 (LSM) powders, with x ∼ 0.15, were synthesized with the epoxide addition sol−gel method. Through this simple technique, sol−gel materials were prepared from methanolic solutions of metal chlorides without the need for alkoxides, polymeric gel agents, or elaborate reaction schemes. The gels were dried in ambient conditions, resulting in mesoporous xerogels with networked nanostructures interconnecting particulate regions. Calcination of the dried gels resulted in the crystallization of single-phase LSM by 700 °C, after decomposition of intermediate hydroxide, chloride, and oxychloride compounds. SEM analysis indicated that the calcined powders were nanocrystalline and consisted of discrete particles, free of hard agglomeration. The average crystallite size and equivalent spherical diameter determined from XRD line broadening and BET analysis, respectively, were in good agreement with the SEM results (∼100 nm). The activation energies for the electronic conductivity...

Thermoelectric materials provide a key solution to energy problems through the conversion of heat into electrical energy. We report that the complex Zintl compound, Yb14MnSb11, breaks a 2-decade stagnation in high-temperature (>900 K), p-type materials development for thermoelectric power generation. This material achieves quadrupled efficiency and virtually doubled figure of merit over the current state-of-the-art, SiGe, thus earmarking it superior for thermoelectric applications in segmented devices. Yb14MnSb11 represents the first complex Zintl phase with substantially higher figure of merit and efficiency than any other competing materials, opening a new class of thermoelectric compounds with remarkable chemical and physical properties.

Various reaction conditions, such as reductant, time, procedure, concentration, and temperature, were investigated with the aim of finding a simple, optimized synthetic route for the synthesis of crystalline germanium nanoparticles. Results from these studies indicate that sodium naphthalide is an ideal reductant and that the reaction is virtually complete within 10 min. Furthermore, it was observed that a two-pot synthesis resulted in a cleaner, narrower distribution of nanoparticle size and that the narrowest size distribution (∼20%) was produced when a dilute Na(naphth) in glyme mixture was utilized. The optimum initial reduction temperature was found to be 0 °C. It was also shown that concentration and temperature play an important role in controlling nanoparticle size. The best reaction conditions, as stated above, produced nanoparticles with a size dispersion of ∼20% when combined. Transmission electron microscopy (TEM), selected-area electron diffraction (SAED), high-resolution TEM (HRTEM), energy-...

Single crystals of a new Zintl compound, EuIn2P2, were grown from indium metal as a flux solvent. The compound crystallizes in the hexagonal P6(3)/mmc space group with a unit cell of a = 4.0829(6) A, c = 17.595(4) A, and Z = 2. It contains alternating Eu2+ layers and [In2P2]2- layers. This compound is paramagnetic at high temperatures with a magnetic transition at 24 K. In the magnetically ordered state, it shows large magnetic anisotropy. The temperature-dependent resistivity of this compound suggests interaction between conduction electrons and local spins. Negative colossal magnetoresistance of up to −398% (MR = {[ρ(H) − ρ(0)]/ρ(H)} × 100%) at 5 T is observed at 24 K.

Butyl-capped crystalline germanium (Ge) nanoparticles were synthesized at room temperature in dimethoxyethane by reduction of GeCl4 with Na(naphthalide) and subsequent reaction with butyl Grignard. The nanoparticles were isolated in hexane and characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDX), elemental analysis, and X-ray powder diffraction (XRD). The product from this room-temperature reaction was heated under vacuum at temperatures of 200−600 °C at 50 °C intervals. The product obtained from the 300 °C treatment was soluble in hexane, while the products from temperatures greater than 300 °C were not. SAED was consistent with crystalline Ge from the initial synthesis at room temperature and amorphous Ge for the product heated under vacuum to 300 °C. X-ray powder diffraction of the 300 °C product shows the transition from amorphous to crystalline nanoparticles occurring between 550 and 600 °C. TEM shows that the n...

Homogeneous, nanocrystalline powders of yttria-stabilized zirconia (YSZ) were prepared using a non-alkoxide sol−gel method. Monolithic gels, free of precipitation, were prepared by addition of propylene oxide to aqueous solutions of Zr4+ and Y3+ chlorides at room temperature. The gels were dried with supercritical CO2(l), resulting in amorphous aerogels that crystallized into stabilized ZrO2 following calcination at 500 °C. The aerogels and resulting crystalline products were characterized using in situ temperature profile X-ray diffraction, Raman spectroscopy, thermal analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption/desorption analysis, and elemental analysis by inductively coupled plasma-atomic emission spectroscopy. TEM and N2 adsorption/desorption analysis of an aerogel prepared by this method indicated a porous network structure with a high surface area (409 m2/g). The crystallized YSZ maintained high surface area (159 m2/g) upon formation of h...

Alkyl-capped and alkyl/alkoxy-capped silicon nanocrystals have been prepared by the oxidation of magnesium silicide with bromine. High-resolution transmission electron microscopy confirmed the crystalline nature of the nanoparticles and provided an average diameter of 4.5 (2.0) nm for the alkyl-capped and for the alkyl/alkoxy-capped nanoparticles. Energy-dispersive X-ray spectroscopy showed that the nanoparticles are composed of silicon, with no evidence of unreacted bromine. FTIR spectra were consistent with alkyl- and alkyl/alkoxy-capped surfaces. Fluorescence spectroscopy indicated strong ultraviolet-blue photoluminescence, which was attributed to both quantum confinement and surface termination. These nanoparticles displayed long-term stability and no degradation of the photoluminescence was observed for a period of 1 year.

The solid solution of the ternary transition metal Zintl phase Ca 14-x Eu x MnSb 11 (0 < x < 14) has been prepared by heating a mixture of stoichiometric amounts of the elements in a two-zone furnace with T high = 1100 °C and T low = 1050 °C. The ternary transition metal compounds crystallize in the tetragonal space group I4 1 /acd and are isostructural with the Zintl compound Ca 14 AlSb 11 . The lattice parameters of the Ca 14-x Eu x MnSb 11 compounds linearly increase with increasing Eu substitution for Ca. The Eu atoms preferentially occupy the C a (2) site first and subsequently occupy Ca(4), Ca(1), and Ca(3), in order, among the four crystallographically inequivalent Ca sites. Temperature-dependent magnetic susceptibility measurements of the solid solution reveal that Eu replacement for Ca induces complex magnetic interactions in the compound, from simple ferromagnetic interactions for Ca 14 -MnSb 11 to ferrimagnetic interactions for Eu 14 MnSb 11 , because of the Eu 2+ (4f 7 ) magnetic moment. The paramagnetic Curie temperature of the Ca 14-x Eu x MnSb 11 compounds shows an interesting change with varying x, and the magnetic easy axis gradually changes in the solid solution from perpendicular (for Ca 14 MnSb 11 ) to parallel (for Eu 14 MnSb 11 ) to the crystal c axis. The electrical transport properties of the Ca 14-x Eu x MnSb 11 (x = 0, 3, 11) compounds show a close relation to their magnetic properties and are compared to the previous results for Ca 14-x Eu x MnSb 11 (x = 13, 14). The influence of Eu doping on the structural and physical property of Ca 14-x Eu x MnSb 11 is discussed in terms of the site preferences of Eu for the four different Ca sites.

The compounds Ca14AlP11, Ca14MnP11, and Eu14MnP11 have been synthesized and are isostructural to the Zintl compound, Ca14AlSb11. Eu14MnP11 is a ferromagnet showing colossal magnetoresistance at TC = 52 K, Ca14MnP11 shows paramagnetic behavior down to 5 K, and Ca14AlP11 is nonmagnetic. The formula unit for these Zintl compounds is A14MPn11 and comprises 14 A cations, a MPn4 tetrahedron, four isolated Pn anions, and a Pn3 linear unit. The central Pn of the Pn3 unit is believed to be positionally disordered, and it has been speculated that the disorder is static rather than dynamic. To address this issue, 31P solid-state NMR was applied to these new compounds to provide insight into the magnetic ordering and structural changes. The NMR chemical shift anisotropy and the dipolar coupling for the 31P nuclei as well as the quadrupolar coupling for the 27Al nucleus in the diamagnetic compound Ca14AlP11 provide structural details consistent with the Zintl structure. Wide-line 31P NMR and EPR were applied to the pa...

The effect of four different dopants (Ca, Sr, Ba, and Yb) on the structural and physical properties of the ternary rare-earth transition metal compound, Eu14MnSb11, has been investigated. The compounds, Eu14-xAxMnSb11 (A = Ca, Sr, Ba, and Yb, x = 1), have been prepared by heating the mixture of stoichiometric amounts of the elements, sealed in a quartz jacketed Ta tube, in a two-zone furnace with Thigh = 1100 °C and Tlow = 1050 °C for 10 days. These compounds are isostructural with the Zintl compound Ca14AlSb11 and crystallize in the tetragonal space group I41/acd, Z = 8. The lattice parameters of the doped compound increase correspondingly as the radius of the metal dopant (A2+) increases. The preference of the dopants onto the four crystallographically inequivalent sites of Eu was examined by single-crystal X-ray diffraction. The magnetization of the compounds has been measured as a function of temperature and applied magnetic field. Temperature-dependent magnetic susceptibility measurement of powder sa...

The compounds, Eu14-xCaxMnSb11 (x < 3), have been prepared by heating the mixture of stoichiometric amounts of the elements, sealed in a quartz-jacketed Ta tube, in a two-zone furnace with Thigh = ...

The compounds Na2Ti2Pn2O (Pn = As, Sb) crystallize in the anti-K2NiF4 structure type in the space group, I4/mmm, with Z = 2 and the lattice parameters a = 4.0810(9) A and c = 15.311(3) A for the As analogue at 310 K and a = 4.160(2) A and c = 16.558(7) A for the Sb analogue at 150 K. The structure consists of edge-shared [Ti4/2Pn2O4/4]2- layers separated by double layers of Na+. These compounds exhibit an anomalous transition in the temperature-dependent magnetic susceptibility at = 330 K for the As analogue and = 120 K for the Sb analogue. Temperature-dependent powder neutron diffraction has been performed to investigate the magnetic spin ordering and structure symmetry breakdown of the compounds; however, no scattering due to magnetic spin ordering or symmetry change has been detected. The temperature-dependent electrical resistivity of these compounds also exhibits an anomaly reminiscent of CDW (charge-density-wave)/SDW (spin-density-wave) materials. The As analogue shows an insulator-to-insulator tran...

The new compounds Eu14MnAs11 and Eu14MnP11 were synthesized from stoichiometric amounts of the elements. The compounds are isotypic to Ca14AlSb11 and crystallize in the tetragonal space group I41/acd (Z = 8). Lattice parameters obtained from single-crystal X-ray diffraction at 130 K are a = 16.318 (2) A, c = 21.684 (4) A and a = 15.930 (4) A, c = 21.213 (5) A for Eu14MnAs11 and Eu14MnP11, respectively. In the refinement of each structure, the central Pn(4) site of a Pn37- linear unit (Pn = As, P) shows positional disorder; this is in contrast to the ordered structures formed when Pn = Sb and Bi. Eu14MnAs11 and Eu14MnP11 are ferromagnetic with transitions at 74 and 52 K, respectively. Eu14MnAs11 also has a low-temperature transition at ∼25 K. Resistivity measurements indicate an insulator-to-metal transition near the magnetic transition, and plots of ln ρ vs 1/T are linear above TC, providing activation energies of 0.03 eV (As; 240−300 K) and 0.31 eV (P). The resistivity is suppressed in the presence of a ...

The new pnictide oxide Sr2MnZn2As2O2 is reported. The crystal structure of this compound consists of a 1:1 intergrowth of square-planar MnO22- layers and ThCr2Si2-type Zn2As22- layers interspersed by Sr cations. This compound has been prepared by sintering the stoichiometric ratio of SrO, Mn, Zn, and As in a fused-silica ampule under 0.2 atm of Ar at 1000 °C for 1 week. The sample quality has been examined by Rietveld refinement of the powder X-ray diffraction data, and the transition metal site (2a and 4d) selectivity has been analyzed by Rietveld refinement of powder neutron diffraction data. Furthermore, effects of this structural order on the magnetic susceptibility and interaction between the magnetic layers have been analyzed by temperature-dependent magnetization measurements. The magnetic structures of both phases, A2MnZn2As2O2 (A = Sr, Ba), have been investigated by temperature-dependent powder neutron diffraction. The Ba analogue exhibits two-dimensional short-range order below about 40 K, where...

The synthesis of silicon nanoclusters and their characterization by multinuclear solid-state nuclear magnetic resonance (NMR) is presented. A combination of 23Na, 29Si, and 13C magic angle spinning with and without cross polarization to 1H nuclei have been used to investigate the reaction of sodium silicide (NaSi) with silicon tetrachloride (SiCl4) followed by varying degrees of surface passivation. The 23Na and 29Si NMR spectra of NaSi distinguish the two crystallographically inequivalent sites for each, consistent with the crystal structure. This compound exhibits extreme diamagnetic chemical shifts for 29Si of −361 and −366 ppm. NaSi is reacted with SiCl4 in refluxing ethylene glycol dimethyl ether to produce both amorphous and crystalline Si nanoparticles with surfaces capped by chlorine. This reaction produces new 29Si resonances that survive subsequent capping and oxidation reactions. The 29Si NMR spectrum shows that the product is incompletely passivated with butyl groups and gives several peaks ly...

Nanometer-sized tin, Sn/R, and Sn/Si−R (R = n-C4H9), core/shell nanoparticles have been prepared by the reaction of SnCl4 or SiCl4 with Mg2Sn in ethylene glycol dimethyl ether (glyme) and subsequently with n-C4H9Li. Sn/SiO2 core/shell nanoparticles are produced from the reaction of Mg2Sn with SiCl4 and subsequent reaction with H2O2. Fourier transform Infrared (FTIR) spectra are consistent with n-butyl surface termination for the n-butyl-capped tin (Sn/n-butyl) and the silicon-n-butyl capped tin (Sn/Si-n-butyl) core/shell nanoparticles. High-resolution transmission electron microscope (HRTEM) confirms that the core part of Sn/n-butyl and Sn/Si- n-butyl nanoparticles is consistent with the tetragonal structure of tin, exhibiting lattice fringes of the {200} crystal plane (2.92 A). The FTIR spectrum of Sn/SiO2 confirms the evidence of silica capping and selected area electron diffraction (SAED) is consistent with an amorphous shell (SiO2) and crystalline Sn core. Solid-state nuclear magnetic resonance (NMR) ...

Ge/Si−R and Ge/SiO2 core−shell nanoparticles have been synthesized by a solution route from the stepwise reactions of the Zintl salt, Mg2Ge, with SiCl4 and subsequently either RLi (R = butyl) or H2O2. High-resolution transmission electron microscopy (HRTEM) images show that the core part of these Ge/Si−R and Ge/SiO2 nanoparticles is crystalline and the d spacing of lattice fringes agrees with the {111} crystal plane (3.27 A) of Ge. The average sizes (diameter) are 5.8(2.3) and 6.8(2.8) nm for Ge/Si−R and Ge/SiO2, respectively. Fourier transform−infrared (FTIR) spectra are consistent with alkyl groups bonded to the silicon surface in Ge/Si−R nanoclusters. Off-axis holography was performed for several Ge/SiO2 nanoparticles. The characterization of the ratio of radii and geometry between the core part and the outer sphere of Ge/SiO2 is presented. The reconstructed phase image from the hologram offers detailed information concerning the ratio of the shell thickness (R − r) to the radius of the core (r), Rr = ...

A solution synthesis of crystalline Ge nanoparticles (nc-Ge ) is reported. The metathesis reaction of NaGe with excess GeCl4 in glyme solvents produces nc-Ge. Metathesis reactions between KGe and excess GeCl4 or GeCl2:(dioxane) in glyme and Mg2Ge and excess GeCl4 in diglyme and triglyme were also investigated. The surface of these nanoparticles is terminated with alkyl groups by reaction with alkyl Li and Grignard reagents. The alkyl-terminated crystalline Ge nanoparticles (R-nc-Ge) were characterized by Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy, powder X-ray diffraction, UV−vis absorption spectroscopy, photoluminescence, and photoluminescence excitation spectroscopy. The optical properties of R-nc-Ge made by this method agree with predictions from quantum confinement models.

We have studied the electronic properties of Zintl phase KSi, by the ab initio density functional pseudopotential method. Our interest in this Zintl compound is in its current use as a reagent in the synthesis of Si nanoclusters. The structure consists of isolated Si4 tetrahedra with K atoms situated above each face. The crystal system is cubic with the symmetry of the P43m space group. Band structure calculations show a band gap of 1.3 eV. The presence of K atoms has widened the band gap over that found between occupied and unoccupied energy levels in the Si4 cluster. The valence bandwidth lies between the valence bandwidth of crystalline Si with diamond structure and the width of the occupied energy levels of the Si4 cluster. The density of states shows four major structures for the occupied bands. The lowest energy band of conduction states is also given in the density of states plot. The nature of the bonding in the crystal is revealed by an examination of the charge density associated with each of t...

Rare-earth transition metal compounds Yb14MnSb11 and Yb14MnBi11 have been prepared by heating stoichiometric amounts of the elements at 1000−1200 °C. 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 (143 K) were refined for Yb14MnSb11 [a = 16.615(2) A, c = 21.948(4) A, V = 6059(2) A3, and R1/wR2 (0.0299/0.0479)] and Yb14MnBi11 [a = 17.000(3) A, c = 22.259(6) A, V = 6433(2) A3, R1/wR2 (0.0631/0.133)]. Structural analysis is consistent with Yb2+. Temperature-dependent magnetic susceptibility data show that Yb14MnSb11 orders ferromagnetically at 56 K and Yb14MnBi11 has a ferromagnetic transition at 58 K and another transition at 28 K. High-temperature magnetic susceptibility data can be fit with a modified Curie−Weiss law and give μeff = 4.92(2)μB and μeff = 4.9(1)μB for the Sb and Bi compounds, respectively. This result is consistent with the assignment of Mn3+ (d4) and Yb2+ (f 14). Single-crystal ma...

A new mixed transition metal pnictide oxide, Ba2MnZn2As2O2, is reported. Ba2MnZn2As2O2 has been prepared in quantitative yield from heating stoichiometric amounts of BaO with the elements, which ar...