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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Rapid Solidification Effects in Additively Manufactured Si and SiGe Compositions

SiGe alloys have a proven track record as robust high-temperature thermoelectric materials, powering NASA missions like SNAP-10A, LES-9, and Voyager 1 and 2. Enhancing thermoelectric efficiency hinges on minimizing thermal conductivity while preserving electrical conductivity. Rapid solidification via LPBF can generate microstructural features such as subgrain cellular boundaries and twinning, which may help reduce thermal conductivity while preserving semiconducting behavior. Here, this study investigates the potential of laser powder bed fusion (LPBF) additive manufacturing to fabricate nanostructured Si and SiGe thermoelectric materials. High cooling rates (10 5 to 10 7 K/s) rates inherent to the LPBF process are conducive to forming such nanostructures. Moreover, this fabrication technique could also be suitable for fabricating complex geometries needed to achieve improved device level performance. Process mapping of commercial Si powder with irregular morphology was first performed to understand the LPBF processing behavior of this semiconductor material. Subsequent studies included in-house synthesized B-doped (p-type) Si7 8 Ge 22 spherical powder that was produced via ultrasonic atomization. Scan strategies involved multiple laser exposures to mitigate solidification cracking: a high density of >98% was achieved, but solidification cracking could not be fully eliminated. Subsequently, a high electrical resistivity (i.e., low conductivity) was observed, but the measured Seebeck coefficient, ∼230 μV/K @ 500 °C, proved that good semiconductor material was being fabricated. A subgrain cellular structure (5–10 μm) was observed as defined by Ge segregation to the intercellular boundaries. The remelting strategies helped lower the cooling rates in processing SiGe, but this still resulted in high residual stresses, which induced a remarkably high density of twins (78–95%) to accommodate the deformation. This unique grain structure offers an avenue for phonon scattering and potential improvements in thermoelectric performance.

figure of merit↗
DOE OSTI2017

Thermoelectric transport properties of BaBiTe{sub 3}-based materials

BaBiTe{sub 3}, a material with low thermal conductivity, is an inferior thermoelectric material due to the poor electrical properties originated from its narrow band gap. We choose two types of dopants, K and La, trying to optimize its electrical transport properties. The minority carriers, which harm the Seebeck coefficient in this system, are suppressed by La doping. With the increase of both electrical conductivity and Seebeck coefficient, the power factor of 3% La doped BaBiTe{sub 3} reaches 3.7 μW cm{sup −1} K{sup −2} which increased by 40% from undoped BaBiTe{sub 3}. Besides high power factor, the thermal conductivity is also reduced in it. Eventually, a high ZT value, 0.25 at 473 K, for n-type BaBiTe{sub 3} is achieved in 3% La doped BaBiTe{sub 3}. - Graphical abstract: BaBiTe{sub 3} possesses a low thermal conductivity. However, it is an inferior thermoelectric material due to the poor electrical properties originated from its narrow band gap. A high ZT value of 0.25 at 473 K for n-type BaBiTe{sub 3} can be achieved through optimizing electrical transport properties via La doping. - Highlights: • BaBiTe{sub 3} is an analogue of these promising thermoelectric materials: such as CsBi{sub 4}Te{sub 6} and K{sub 2}Bi{sub 8}Se{sub 13}, etc. • BaBiTe{sub 3} possesses a low thermal conductivity. • La is an effective dopant to enhance electrical transport properties. • A high ZT value of 0.25 at 473 K can be achieved in n-type La-doped BaBiTe{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The synthesis of CuO and NiO nanoparticles by facile thermal decomposition of metal-Schiff base complexes and an examination of their electric, thermoelectric and magnetic Properties

Highlights: • Thermal decomposition of Schiff base complexes provides a convenient and effective pathway to fabricate CuO and NiO NPs. • The electrical conduction in CuO NPs and NiO NPs is governed by intrinsic band-to-band type and large polarons conduction mechanism, respectively. • The thermoelectric measurements confirm that the NPs are P-type degenerate semiconductors. • The NPs show weak ferromagnetic ordering at room temperature and antiferromagnetic to paramagnetic transition with high dipolar interaction. - Abstract: In this study, CuO and NiO NPs have been synthesized by facile thermal decomposition of Schiff base complexes and their physical properties have been examined. The synthesized CuO and NiO NPs are crystallized in polycrystalline monoclinic and cubic structures with average particle size 17 ± 0.4 and 62 ± 1 nm, respectively. The electrical conductivity measurements confirm that the conduction in the CuO NPs is a band-to-band type while the conduction in the NiO NPs is governed by the large polaron conduction mechanism. The thermoelectric measurements confirm that the CuO and NiO NPs are P-type degenerate semiconductors with room temperature Seebeck coefficients equal to 89.9 and 12.1 mV/K, respectively. The magnetic measurements exhibit that the NPs have weak ferromagnetic ordering and antiferromagnetic to paramagnetic transition with high dipolar interaction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Interference enhanced thermoelectricity in quinoid type structures

Quantum interference (QI) effects in molecular junctions may be used to obtain large thermoelectric responses. We study the electrical conductance G and the thermoelectric response of a series of molecules featuring a quinoid core using density functional theory, as well as a semi-empirical interacting model Hamiltonian describing the π-system of the molecule which we treat in the GW approximation. Molecules with a quinoid type structure are shown to have two distinct destructive QI features close to the frontier orbital energies. These manifest themselves as two dips in the transmission, that remain separated, even when either electron donating or withdrawing side groups are added. We find that the position of the dips in the transmission and the frontier molecular levels can be chemically controlled by varying the electron donating or withdrawing character of the side groups as well as the conjugation length inside the molecule. This feature results in a very high thermoelectric power factor S{sup 2}G and figure of merit ZT, where S is the Seebeck coefficient, making quinoid type molecules potential candidates for efficient thermoelectric devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

“Glass-like” thermal conductivity gradually induced in thermoelectric Sr{sub 8}Ga{sub 16}Ge{sub 30} clathrate by off-centered guest atoms

The origin of the “glass-like” plateau in thermal conductivity of inorganic type I clathrates has been debated for more than a decade. Here, it is demonstrated that the low temperature thermal conductivity of Sr{sub 8}Ga{sub 16}Ge{sub 30} can be controlled by the synthesis method: A flux-grown sample has a “glass-like” plateau in thermal conductivity at low temperature, while a zone-melted sample instead has a crystalline peak. A combination of flux-growth and zone-melting produces an intermediate thermal conductivity. In a comprehensive study of three single crystal samples, it is shown by neutron diffraction that the transition from crystalline peak to “glass-like” plateau is related to an increase in Sr guest atom off-centering distance from 0.24 Å to 0.43 Å. By modifying ab initio calculated force constants for the guest atom to an isotropic model, we reproduce both measured heat capacity and inelastic neutron scattering data. The transition from peak to plateau in the thermal conductivity can be modeled by a combined increase of Rayleigh and disorder scattering. Measurement of heat capacity refutes simple models for tunneling of Sr between off-center sites. Furthermore, the electronic properties of the same samples are characterized by Hall carrier density, Seebeck coefficient, and resistivity. The present comprehensive analysis excludes tunneling and charge carrier scattering as dominant contributors to the “glass-like” plateau. The increased guest atom off-centering distance controlled by synthesis provides a possible microscopic mechanism for reducing the low temperature thermal conductivity of clathrates.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Validation of galvanomagnetic and thermomagnetic transport measurements using Standard Reference Material 3451

In the “method of four coefficients,” electrical resistivity (ρ), Seebeck coefficient (S), Hall coefficient (RH), and Nernst coefficient (Q) of a material are measured and typically fit or modeled with theoretical expressions based on Boltzmann transport theory to glean experimental insights into features of electronic structure and/or charge carrier scattering mechanisms in materials. Although well-defined and readily available reference materials exist for validating measurements of ρ and S, none currently exists for R H or Q. We show that measurements of all four transport coefficients—ρ, S, R H , and Q—can be validated using a single reference sample, namely, the low-temperature Seebeck coefficient Standard Reference Material® (SRM) 3451 (composition Bi 2 Te 3+x ) available from the National Institute for Standards and Technology (NIST) without the need for inter-laboratory sample exchange. Here, R H and Q data for NIST SRM 3451 reported here for the temperature range 80–400 K complement the data already available for ρ and S and will therefore be of interest to researchers desiring to validate new or existing galvanomagnetic and thermomagnetic transport properties measurement systems.

47 OTHER INSTRUMENTATION↗
DOE OSTI2014

Role of phonon scattering by elastic strain field in thermoelectric Sr{sub 1−x}Y{sub x}TiO{sub 3−δ}

Perovskite-type SrTiO{sub 3−δ} ceramics are multifunctional materials with significant potential as n-type thermoelectric (TE) materials. The electronic and thermal transport properties of spark plasma sintered polycrystalline Sr{sub 1−x}Y{sub x}TiO{sub 3−δ} (x = 0.05, 0.075, 0.1) ceramics are systematically investigated from (15–800) K. The Sr{sub 0.9}Y{sub 0.1}TiO{sub 3−δ} simultaneously exhibits a large Seebeck coefficient, α > −80 μV/K and moderately high electrical resistivity, ρ ∼ 0.8 mΩ-cm at a carrier concentration of ∼10{sup 21} cm{sup −3} at 300 K resulting in a high TE power factor defined herein as (α{sup 2}σT) ∼ 0.84 W/m-K at 760 K. Despite the similar atomic masses of Sr (87.6 g/mol) and Y (88.9 g/mol), the lattice thermal conductivity (κ{sub L}) of Sr{sub 1−x}Y{sub x}TiO{sub 3−δ} is significantly reduced with increased Y-doping, owing to the smaller ionic radii of Y{sup 3+} (∼1.23 Å, coordination number 12) compared to Sr{sup 2+} (∼1.44 Å, coordination number 12) ions. In order to understand the thermal conductivity reduction mechanism, the κ{sub L} in the Sr{sub 1−x}Y{sub x}TiO{sub 3−δ} series are phenomenologically modeled with a modified Callaway's equation from 30–600 K. Phonon scattering by elastic strain field due to ionic radii mismatch is found to be the prominent scattering mechanism in reducing κ{sub L} of these materials. In addition, the effect of Y-doping on the elastic moduli of Sr{sub 1−x}Y{sub x}TiO{sub 3−δ} (x = 0, 0.1) is investigated using resonant ultrasound spectroscopy, which exhibits an anomaly in x = 0.1 in the temperature range 300–600 K. As a result, the phonon mean free path is found to be further reduced in the Sr{sub 0.9}Y{sub 0.1}TiO{sub 3−δ} compared to that of SrTiO{sub 3−δ}, resulting in a considerably low thermal conductivity κ ∼ 2.7 W/m-K at 760 K. Finally, we report a thermoelectric figure of merit (ZT) ∼ 0.3 at 760 K in the Sr{sub 0.9}Y{sub 0.1}TiO{sub 3−δ}, the highest ZT value reported in the Y-doped SrTiO{sub 3} ceramics thus far.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Selective modulation of electronic transport in VO 2 induced by 10 keV helium ion irradiation

Vanadium dioxide (VO 2 ) manifests an abrupt metal–insulator transition (MIT) from monoclinic to rutile phases, with potential use for tunable electronic and optical properties and spiking neuromorphic devices. Understanding pathways to modulate electronic transport in VO 2 , as well as its response to irradiation (e.g., for space applications), is critical to better enable these applications. In this work, we investigate the selective modulation of electronic transport in VO 2 films subject to different 10 keV helium ion (He + ) fluences. Under these conditions, the resistivity in the individual monoclinic and rutile phases varied by 50%–200%, while the MIT transformation temperature remains constant within 4 °C independent of irradiation fluence. Importantly, different trends in the resistivity of the monoclinic and rutile phases were observed both as a function of total He fluence as well as in films grown on different substrates (amorphous SiO 2 /Si vs single crystal Al 2 O 3 ). Through a combination of measurements including majority carrier sign via Seebeck, low frequency noise, and TEM, our investigation supports the presence of different kinds of point defects (V in; O in), which may arise due to grain boundary defect interactions. Our work suggests the utility of He irradiation for the selective modulation of VO 2 transport properties for neuromorphic, in contrast to other established but non-selective methods, like doping.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Tuning the charge carrier density in the thermoelectric colusite

The colusite Cu{sub 26}V{sub 2}Sn{sub 6}S{sub 32} has high potential as a thermoelectric material at medium-high temperatures because of a large Seebeck coefficient (S ≃ 220 μV/K) and rather small electrical resistivity (ρ ≃ 100 μΩm) at 660 K. To improve the thermoelectric performance, we have tuned the hole carrier density p by substituting Zn for Cu in Cu{sub 26−x}Zn{sub x}V{sub 2}Sn{sub 6}S{sub 32} (x = 1–3) and starting with Cu and Sn deficient compositions in Cu{sub 26−y}V{sub 2}Sn{sub 6}S{sub 32} (y = 1, 2) and Cu{sub 26}V{sub 2}Sn{sub 6−z}S{sub 32} (z = 0.25–1), respectively. Powder x-ray diffraction and electron-probe microanalysis showed that the Zn-substituted samples and Sn-deficient (z ≥ 0.5) samples are formed in a single phase, whereas the Cu{sub 26−y}V{sub 2}Sn{sub 6}S{sub 32} samples are composed of two phases with slightly different compositions. Within these samples, the value of p at 300 K varies in the range between 3.6 × 10{sup 20} and 2.8 × 10{sup 21 }cm{sup −3}. The relation between p and S led to the effective mass m* of 4–7m{sub 0} for the hole carriers. The large S of the colusite is therefore ascribed to the heavy mass carriers of the valence band top. The decreases in p with x and y reduced the dimensionless thermoelectric figure of merit ZT, whereas the increase in p with z raised ZT from 0.56 (z = 0) to 0.62 (z = 0.5) at 660 K.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2001

Thermal Modeling and Analysis of a Sub-Compact Seebeck Furnace

The Sub-Compact Seebeck Furnace (SCSF) is a third generation furnace designed as an experimental facility to study the phenomena of undercooling associated with directional solidification. It is intended to provide a double peak temperature profile along the axial direction with gradient zones at each end. By keeping the temperature in the central portion above the melting point of the sample, and cooling the ends of the furnace, a solid/liquid (S/L) interface can be maintained in each one of the gradient zones. A motorized motion control provides a motion to one-half of the furnace. The undercooling associated with the interface being directionally solidified can thus be studied. Modeling of the temperature profile is important to help assure that the furnace design provides the correct thermal characteristics. The furnace is designed with two halves that telescope. Results of thermal analysis based on an analytical solution using simple assumptions will be presented. The resulting temperature profile will show the salient features of the desired thermal profile and provide the general directions for thermal design. Experimental results will be used to compare with the analytical profile. Approach for numerical modeling to provide more detailed information such as two-dimensional effects will be discussed.

Wang, Francis C.↗
DOE OSTI2018

Structural Changes as a Function of Thickness in [(SnSe) 1+δ ] m TiSe 2 Heterostructures

Single- and few-layer metal chalcogenide compounds are of significant interest due to structural changes and emergent electronic properties on reducing dimensionality from three to two dimensions. To explore dimensionality effects in SnSe, a series of [(SnSe) 1+δ ] m TiSe 2 intergrowth structures with increasing SnSe layer thickness (m = 1-4) were prepared from designed thin-film precursors. In-plane diffraction patterns indicated that significant structural changes occurred in the basal plane of the SnSe constituent as m is increased. Scanning transmission electron microscopy cross-sectional images of the m = 1 compound indicate long-range coherence between layers, whereas the m >/= 2 compounds show extensive rotational disorder between the constituent layers. For m >/= 2, the images of the SnSe constituent contain a variety of stacking sequences of SnSe bilayers. Density functional theory calculations suggest that the formation energy is similar for several different SnSe stacking sequences. The compounds show unexpected transport properties as m is increased, including the first p-type behavior observed in (MSe)m(TiSe 2 ) n compounds. The resistivity of the m >/- 2 compounds is larger than for m = 1, with m = 2 being the largest. At room temperature, the Hall coefficient is positive for m = 1 and negative for m = 2-4. The Hall coefficient of the m = 2 compound changes sign as temperature is decreased. The room-temperature Seebeck coefficient, however, switches from negative to positive at m = 3. These properties are incompatible with single band transport indicating that the compounds are not simple composites.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Correlation between processing conditions, microstructure and charge transport in half-Heusler alloys

Five bulk samples of n-type Zr₀.₂₅Hf₀.₇₅NiSn₀.₉₇₅Sb₀.₀₂₅ half-Heusler (HH) alloy were fabricated by reacting elemental powders via (1) high temperature solid state (SS) reaction and (2) mechanical alloying (MA), followed by densification using spark plasma sintering (SPS) and/or hot pressing (HP). A portion of the sample obtained by SS reaction was mechanically alloyed before consolidation by hot pressing (SS–MA–HP). X-ray powder diffraction and transmission electron microscopy studies revealed that all SS specimen (SS–SPS, SS–HP, SS–MA–HP) are single phase HH alloys, whereas the MA sample (MA–SPS) contains metallic nanoprecipitates. Electronic and thermal transport measurements showed that the embedded nanoprecipitates induce a drastic increase in the carrier concentration (n), a large decrease in the Seebeck coefficient (S) and a marginal decrease in the lattice thermal conductivity (κ l ) of the MA–SPS sample leading to lower ZT values when compared to the SS–HP samples. Constant values of S are observed for the SS series regardless of the processing method. However, a strong dependence of the carrier mobility (μ), electrical conductivity (σ) and κ l on the processing and consolidation method is observed. For instance, mechanical alloying introduces additional structural defects which enhance electron and phonon scattering leading to moderately low values of μ and large reduction in κ l . This results in a net 20% enhancement in the figure of merit (ZT=0.6 at 775 K). HH specimen of the same nominal composition with higher ZT is anticipated from a combination of SS reaction, MA and SPS (SS–MA–SPS). - Graphical abstract: In half-Heusler alloys, thermopower values are insensitive to processing method, whereas carrier mobility (μ), electrical conductivity (σ), and κ l strongly dependent on the microstructure which in turn is altered by the synthesis, processing and consolidation method. Highlights: • Phase composition of HH alloy strongly depends on the synthesis technique. • Mechanical alloying of elements yields bulk HH alloy with metallic impurity phases. • Thermopower, carrier density, and effective mass of HHs are insensitive to processing conditions. • Mechanical alloying decreases the carrier mobility and lattice thermal conductivity of bulk HH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ba-filled Ni–Sb–Sn based skutterudites with anomalously high lattice thermal conductivity

Here, in this study, novel filled skutterudites Ba y Ni 4 Sb 12-x Sn x (y max = 0.93) have been prepared by arc melting followed by annealing at 250, 350 and 450°C up to 30 days in vacuum-sealed quartz vials. Extension of the homogeneity region, solidus temperatures and structural investigations were performed for the skutterudite phase in the ternary Ni–Sn–Sb and in the quaternary Ba–Ni–Sb–Sn systems. Phase equilibria in the Ni–Sn–Sb system at 450°C were established by means of Electron Probe Microanalysis (EPMA) and X-ray Powder Diffraction (XPD). With rather small cages Ni 4 (Sb,Sn) 12 , the Ba–Ni–Sn–Sb skutterudite system is perfectly suited to study the influence of filler atoms on the phonon thermal conductivity. Single-phase samples with the composition Ni 4 Sb 8.2 Sn 3.8 , Ba 0.42 Ni 4 Sb 8.2 Sn 3.8 and Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 were used to measure their physical properties, i.e. temperature dependent electrical resistivity, Seebeck coefficient and thermal conductivity. The resistivity data demonstrate a crossover from metallic to semiconducting behaviour. The corresponding gap width was extracted from the maxima in the Seebeck coefficient data as a function of temperature. Single crystal X-ray structure analyses at 100, 200 and 300 K revealed the thermal expansion coefficients as well as Einstein and Debye temperatures for Ba 0.73 Ni 4 Sb 8.1 Sn 3.9 and Ba 0.95 Ni 4 Sb 6.1 Sn 5.9 . These data were in accordance with the Debye temperatures obtained from the specific heat (4.4 K < T < 140 K) and Mössbauer spectroscopy (10 K < T < 290 K). Rather small atom displacement parameters for the Ba filler atoms indicate a severe reduction in the “rattling behaviour” consistent with the high levels of lattice thermal conductivity. The elastic moduli, collected from Resonant Ultrasonic Spectroscopy ranged from 100 GPa for Ni 4 Sb 8.2 Sn 3.8 to 116 GPa for Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 . The thermal expansion coefficients were 11.8 × 10 -6 K -1 for Ni 4 Sb 8.2 Sn 3.8 and 13.8 × 10 -6 K -1 for Ba 0.92 Ni 4 Sb 6.7 Sn 5.3 . The room temperature Vickers hardness values vary within the range from 2.6 GPa to 4.7 GPa. Lastly, severe plastic deformation via high-pressure torsion was used to introduce nanostructuring; however, the physical properties before and after HPT showed no significant effect on the materials thermoelectric behaviour.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthesis, crystal structure and electrical properties of the tetrahedral quaternary chalcogenides CuM{sub 2}InTe{sub 4} (M=Zn, Cd)

Quaternary chalcogenides form a large class of materials that continue to be of interest for energy-related applications. Certain compositions have recently been identified as possessing good thermoelectric properties however these materials typically have the kesterite structure type with limited variation in composition. In this study we report on the structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} which crystallize in the modified zinc-blende crystal structure, and compare their properties with that of CuZn{sub 2}InSe{sub 4}. These p-type semiconductors have direct band gaps of about 1 eV resulting in relatively high Seebeck coefficient and resistivity values. This work expands on the research into quaternary chalcogenides with new compositions and structure types in order to further the fundamental investigation of multinary chalcogenides for potential thermoelectrics applications. - Graphical abstract: The structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. The unique crystal structure allows for relatively good electrical transports and therefore potential for thermoelectric applications. - Highlights: • The physical properties of CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. • These materials have potential for thermoelectric applications. • Their direct band gaps also suggest potential for photovoltaics applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Leveraging electron-phonon interaction to enhance the thermoelectric power factor in graphene-like semimetals

Electron-phonon interactions (EPIs) are presumably detrimental for thermoelectric performance in semiconductors because they limit carrier mobility. Here we show that enhanced EPIs with strong energy dependence offer an intrinsic pathway to a significant increase in the Seebeck coefficient and the thermoelectric power factor, particularly in the context of two-dimensional (2D) graphene-like Dirac bands. The increase is realized by enabling electron energy filtering through preferential scattering of electron/hole carriers. We prove this concept by implementing first-principles computational methods with explicit treatment of EPIs for a 2D gapless MoS 2 allotrope, which has both massless Dirac bands and a heavy-fermion state that acts as the filter. We determine that the optimal location of the heavy state and hence the onset of the filtering process is at the Dirac point. Our study opens an avenue for attaining ultrahigh power factors via engineering the EPIs in graphene-like semimetals or identifying new compounds that intrinsically possess the featured electronic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Evolution of structure and transport properties of the Ba 8 Cu 16 P 30 clathrate-I framework with the introduction of Ga

Two type-I clathrates were synthesized by introducing Ga into the framework of the Ba 8 Cu 16 P 30 type-I clathrate. The introduction of minute amounts of Ga, 1.9% Ga/M total (where M total = Cu + Ga), resulted in the disturbance of the completely ordered Pbcn superstructure of Ba 8 Cu 16 P 30 . Ba 8 Cu 15.43(2) Ga 0.3 P 30.26(3) crystallizes in a partially ordered orthorhombic Pmna clathrate-I superstructure with five out of 15 framework sites being jointly occupied by metal+phosphorus. Increasing the Ga content resulted in all framework sites being occupied by metal + phosphorus in the archetype cubic Pm n clathrate-I crystal structure of Ba 8 Cu 14.5(3) Ga 1.3 P 30.2(4) with 8.2% Ga/M total . A combination of energy dispersive x-ray spectroscopy, inductively coupled plasma mass spectroscopy, and single crystal x-ray diffraction was used to determine the structures alongside the compositions. The positional disorder was verified by 31 P solid state NMR spectroscopy. Characterization of the transport properties indicated that the Ga-substituted samples exhibit higher Seebeck coefficients and electrical resistivities compared to its pristine counterpart, in line with the expected reduction of the hole concentration due to Ga/Cu substitution. Moderate improvements in the thermoelectric power factor and overall figure-of-merit were observed for samples with 6.9% and 3.8% Ga/M total as compared to those for the pristine Ba 8 Cu 16 P 30 clathrate. Finally, band structure calculations shed light on how Ga substitution affects the electronic structure and thermoelectric properties of studied clathrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

From n- to p-type material: Effect of Metal Ion on Charge Transport in Metal-Organic Materials

An intriguing new class of two-dimensional (2D) materials based on metal–organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a-Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗