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  1. Exciton photoluminescence is observed in disordered zinc tin nitride as a result of benign defect complex formation encouraged by annealing.
  2. Emerging photovoltaic materials need to prove their viability by demonstrating excellent electronic properties. In ternary and multinary semiconductors, disorder and off-stoichiometry often cause defects that limit the potential for high-efficiency solar cells. We report on Zn-rich ZnSnN 2 (Zn/(Zn + Sn) = 0.67) photoluminescence, high-resolution X-ray diffraction, and electronic structure calculations based on Monte-Carlo structural models. The mutual compensation of Zn excess and O incorporation affords a desirable reduction of the otherwise degenerate n-type doping, but also leads to a strongly off-stoichiometric and disordered atomic structure. It is therefore remarkable that we observe only near-edge photoluminescence from well-resolved excitons andmore » shallow donors and acceptors. Based on first principles calculations, this result is explained by the mutual passivation of Zn Sn and O N defects that renders both electronically benign. The calculated bandgaps range between 1.4 and 1.8 eV, depending on the degree of non-equilibrium disorder. The experimentally determined value of 1.5 eV in post-deposition annealed samples falls within this interval, indicating that further bandgap engineering by disorder control should be feasible via appropriate annealing protocols.« less
  3. Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less
  4. High-throughput calculations (first-principles density functional theory and semi-empirical transport models) have the potential to guide the discovery of new thermoelectric materials. Herein we have computationally assessed the potential for thermoelectric performance of 145 complex Zintl pnictides. Of the 145 Zintl compounds assessed, 17% show promising n-type transport properties, compared with only 6% showing promising p-type transport. We predict that n-type Zintl compounds should exhibit high mobility μ n while maintaining the low thermal conductivity κ L typical of Zintl phases. Thus, not only do candidate n-type Zintls outnumber their p-type counterparts, but they may also exhibit improved thermoelectric performance. Frommore » the computational search, we have selected n-type KAlSb 4 as a promising thermoelectric material. Synthesis and characterization of polycrystalline KAlSb 4 reveals non-degenerate n-type transport. With Ba substitution, the carrier concentration is tuned between 10 18 and 10 19 e cm –3 with a maximum Ba solubility of 0.7% on the K site. High temperature transport measurements confirm a high μ n (50 cm 2 V –1 s –1) coupled with a near minimum κ L (0.5 W m –1 K –1) at 370 °C. Together, these properties yield a zT of 0.7 at 370 °C for the composition K 0.99Ba 0.01AlSb 4. As a result, based on the theoretical predictions and subsequent experimental validation, we find significant motivation for the exploration of n-type thermoelectric performance in other Zintl pnictides.« less
  5. In this paper, we present an exfoliation method that produces cm 2-area atomically flat surfaces from bulk layered single crystals, with broad applications such as for the formation of lateral heterostructures and for use as substrates for van der Waals epitaxy. Single crystals of Bi 2Se 3 were grown using the Bridgman method and examined with X-ray reciprocal space maps, Auger spectroscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. An indium-bonding exfoliation technique was developed that produces multiple ~100 um thick atomically flat, macroscopic (>1 cm 2) slabs from each Bi 2Se 3 source crystal. Two-dimensional X-ray diffraction and reciprocalmore » space maps confirm the high crystalline quality of the exfoliated surfaces. Atomic force microscopy reveals that the exfoliated surfaces have an average root-mean-square (RMS) roughness of ~0.04 nm across 400 μm 2 scans and an average terrace width of 70 um between step edges. First-principles calculations reveal exfoliation energies of Bi 2Se 3 and a number of other layered compounds, which demonstrate relevance of our method across the field of 2D materials. While many potential applications exist, excellent lattice matching with the III-V alloy space suggests immediate potential for the use of these exfoliated layered materials as epitaxial substrates for photovoltaic development.« less
  6. The rise of high-throughput calculations has accelerated the discovery of promising classes of thermoelectric materials. In prior work, we identified the n-type Zintl pnictides as one such material class. To date, however, a lack of detailed defect calculations and chemical intuition has led the community to investigate p-type Zintls almost exclusively. Here, we investigate the synthesis, thermoelectric properties, and defect structure of the complex Zintl KGaSb 4. We find that KGaSb 4 is successfully doped n-type with Ba and has the potential for p-type doping with Zn. Our calculations reveal the fundamental defect structure in KGaSb 4 that enables n-typemore » and p-type doping. We find that Ba doped KGaSb4 exhibits high electronic mobility (~50 cm 2V -1s -1) and near minimum lattice thermal conductivity (<0.5 Wm -1K -1) at 400 °C. Samples doped with 1.5% Ba achieve zT > 0.9 at 400 °C, promising for a previously unstudied material. Here, we also briefly investigate the series of alloys between KGaSb 4 and KAlSb 4, finding that a full solid solution exists. Altogether our work reinforces motivation for the exploration of n-type Zintl materials, especially in tandem with high-throughput defect calculations to inform selection of effective dopants and systems amenable to n-type transport.« less
  7. High-throughput, low-cost, and accurate predictions of thermal properties of new materials would be beneficial in fields ranging from thermal barrier coatings and thermoelectrics to integrated circuits. To date, computational efforts for predicting lattice thermal conductivity (κ L) have been hampered by the complexity associated with computing multiple phonon interactions. In this work, we develop and validate a semiempirical model for κ L by fitting density functional theory calculations to experimental data. Experimental values for κ L come from new measurements on SrIn 2O 4, Ba 2SnO 4, Cu 2ZnSiTe 4, MoTe 2, Ba 3In 2O 6, Cu 3TaTe 4, SnO,more » and InI as well as 55 compounds from across the published literature. Here, to capture the anharmonicity in phonon interactions, we incorporate a structural parameter that allows the model to predict κ L within a factor of 1.5 of the experimental value across 4 orders of magnitude in κ L values and over a diverse chemical and structural phase space, with accuracy similar to or better than that of computationally more expensive models.« less

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