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Highly resistive grain boundaries significantly reduce the electrical conductivity that compromises the thermoelectric figure‐of‐merit zT in n‐type polycrystalline Mg_3Sb_2. In this work, discovered is a Mg deficiency near grain boundaries using atom‐probe tomography. Approximately 5 at% of Mg deficiency is observed uniformly in a 10 nm region along the grain boundary without any evidence of a stable secondary or impurity phase. The off‐stoichiometry can prevent n‐type dopants from providing electrons, lowering the local carrier concentration near the grain boundary and thus the local conductivity. This observation explains how nanometer scale compositional variations can dramatically determine thermoelectric zT, and provides concrete strategies to reduce grain‐boundary resistance and increase zT in Mg_3Sb_2‐based materials.

Bi_2Te_3 alloys have been the most widely used n-type material for low temperature thermoelectric power generation for over 50 years, thanks to the highest efficiency in the 300–500 K temperature range relevant for low-grade waste-heat recovery. Here we show that n-type Mg_3Sb_(0.6)Bi_(1.4), with a thermoelectric figure-of-merit zT of 1.0–1.2 at 400–500 K, finally surpasses n-type Bi_2Te_3. This exceptional performance is achieved by tuning the alloy composition of Mg_3(Sb_(1−x)Bi_x)_2. The two primary mechanisms of the improvement are the band effective-mass reduction and grain size enhancement as the Mg_3Bi_2 content increases. The benefit of the effective-mass reduction is only effective up to the optimum composition Mg_3Sb_(0.6)Bi_(1.4), after which a different band dominates charge transport. The larger grains are important for minimizing grain-boundary electrical resistance. Considering the limited choice for low temperature n-type thermoelectric materials, the development of Mg_3Sb_(0.6)Bi_(1.4) is a significant advancement towards sustainable heat recovery technology.

OBJECTIVES: To elucidate predictive factors in the perioperative period resulting in gastrostomy tube (G-tube) dependence for patients undergoing primary surgical treatment of oropharyngeal squamous cell carcinoma (OPSCC) in the modern era. METHODS: Two hundred and thirty patients with known OPSCC treated with primary surgery were screened and selected from a retrospective database spanning from 2002 to 2012 at The Ohio State University Wexner Medical Center (Columbus, Ohio), with univariable and multivariable logistic regression modeling used to determine independent predictive factors resulting in G-tube dependence (defined as tube persistence/presence 1 year after surgery). RESULTS: Surgical approach, baseline characteristics, tumor (T)-nodal-metastasis stage, human papillomavirus status, extent of tissue resected, surgical complications, reconstructive technique, preoperative G-tube presence, and adjuvant treatment were recorded. Patients undergoing open surgery for OPSCC without adjuvant treatment had 42.9% G-tube dependence (44.6% with adjuvant chemoradiation [CRT]) compared to 0% for those undergoing transoral nonrobotic surgery (8.1% with adjuvant CRT) and 0% for those undergoing transoral robotic surgery (10.3% with adjuvant CRT). In multivariable analysis, greater than 25% of the oral tongue resected (odds ratio [OR] 12.29; P = 0.03), an open surgical approach (OR 5.72; P < 0.01) and T3/T4 tumor stage (OR 2.84; P = 0.02) were independent and significant predictors of G-tube dependence. CONCLUSION: Surgical approach, advanced tumor stage, and oral tongue resection may influence the development of nutritional dependence for surgically treated patients with OPSCC. LEVEL OF EVIDENCE: 4.

The charge transport mechanism in a solid is often inferred by observing very simple features like the temperature dependency of electrical conductivity or resistivity. However, comparing complicated physical models to such simple signatures leaves much ambiguity. Because models generally have more parameters than the types of measurements available, inconsistencies can long go unrecognized until the interrelation between different measurements is closely examined. We show that a simple investigation of the thermopower-conductivity relation allows one to phenomenologically characterize transport from experiments; the phenomenologically determined transport function can be compared to physical models to distinguish transport mechanisms and straightforwardly point out inconsistencies in literature models. We highlight two example cases, ceria and strontium titanate, to show that our analysis method can clarify whether the transport mechanism is through hopping or delocalized states. We question previous suggestions about the scattering mechanism in SrTiO_3 and suggest deformation potential scattering on elongated Fermi surfaces as the origin of high-temperature T^2 resistivity.

Thermally activated mobility near room temperature is a signature of detrimental scattering that limits the efficiency and figure-of-merit zT in thermoelectric semiconductors. This effect has been observed dramatically in Mg₃Sb₂-based compounds, but also to a lesser extent in other thermoelectric compounds. Processing samples differently or adding impurities such that this effect is less noticeable produces materials with a higher zT. Experiments suggest that the behavior is related to grain boundaries, but impurity scattering has also been proposed. However, conventional models using Matthissen's rule are not able to explain the dramatic change in the temperature dependency of conductivity or drift mobility which is observed in Mg₃Sb₂-based compounds. We find that it is essential to consider the grain boundary region as an effectively separate phase rather than a scattering center, taking into account the weaker screening in semiconductors compared with classical metals. By modeling a grain boundary phase with a band offset, we successfully reproduce the experimentally observed conductivity versus temperature and thermopower versus conductivity relations, which indicate an improved description of transport. The model shows good agreement with measured grain size dependencies of conductivity, opening up avenues for quantitatively engineering materials with similar behavior. Model estimates predict room for >60% improvement in the room temperature zT of Mg_(3.2)Sb_(1.5)Bi_(0.49)Te_(0.01) if the grain boundary resistance could be eliminated.

Zintl compounds make excellent thermoelectrics with many opportunities for chemically tuning their electronic and thermal transport properties. However, the majority of Zintl compounds are persistently p-type even though computation predicts superior properties when n-type. Surprisingly, n-type Mg₃Sb₂-based thermoelectrics have been recently found with exceptionally high figure of merit. Excess Mg is required to make the material n-type, prompting the suspicion that interstitial Mg is responsible. Here we explore the defect chemistry of Mg₃Sb₂ both theoretically and experimentally to explain why there are two distinct thermodynamic states for Mg₃Sb₂ (Mg-excess and Sb-excess) and why only one can become n-type. This work emphasizes the importance of exploring all of the multiple thermodynamic states in a nominally single-phase semiconductor. This understanding of the existence of multiple inherently distinct different thermodynamic states of the same nominal compound will vastly multiply the number of new complex semiconductors to be discovered for high zT thermoelectrics or other applications.

Mg₃Sb₂–Mg₃Bi₂ alloys show excellent thermoelectric properties. The benefit of alloying has been attributed to the reduction in lattice thermal conductivity. However, Mg₃Bi₂-alloying may also be expected to significantly change the electronic structure. By comparatively modeling the transport properties of n- and p-type Mg₃Sb₂–Mg₃Bi₂ and also Mg₃Bi₂-alloyed and non-alloyed samples, we elucidate the origin of the highest zT composition where electronic properties account for about 50% of the improvement. We find that Mg₃Bi₂ alloying increases the weighted mobility while reducing the band gap. The reduced band gap is found not to compromise the thermoelectric performance for a small amount of Mg₃Bi₂ because the peak zT in unalloyed Mg₃Sb₂ is at a temperature higher than the stable range for the material. By quantifying the electronic influence of Mg₃Bi₂ alloying, we model the optimum Mg₃Bi₂ content for thermoelectrics to be in the range of 20–30%, consistent with the most commonly reported composition Mg₃Sb_(1.5)Bi_(0.5).

Charge transport properties like electrical conductivity or the Seebeck coefficient are defined phenomenologically from near-equilibrium thermodynamics, while the analysis or modeling of them often involves a physical model based on mechanistic principles. In other words, physical models connect microscopic and physical parameters to phenomenological and experimental properties. One of the challenges is that the complexity of solid state requires many physical parameters, whereas the measurable properties which help to determine those parameters are limited. The interrelations of measured properties are very important to overcome this challenge, but this aspect is not well recognized in conventional analysis themes. In this thesis, the concept of using a phenomenological transport function is devised to help combine a collection of measurements into an intermediate level of phenomenology, relevant for Fermion transport but not dependent on a particular physical model. This phenomenological transport function can be determined by examining the electrical conductivity, the Seebeck coefficient, and potentially the Lorenz number. Because the phenomenological transport function combines information from a set of multiple measurable properties, a direct comparison to the transport function of a physical model serves as a strong test for the model. Particular usefulness comes from extracting transport functions from the Seebeck coefficient-conductivity relation, especially in doped semiconductors. This approach is applied to contrast CeO2-x and n-type SrTiO3 as narrow and dispersive transport function materials, each consistent with polaron and band conduction, respectively. In band conductors such as SrTiO3 and Mg3Sb2, the approach is used to test and refute previous claims about the scattering mechanism and find consistency with deformation potential scattering in both cases. In conducting polymers, which do not resemble any other type of conventional conductors, the Seebeck-conductivity relation reveals a qualitative disagreement with the commonly cited Mott's models. For the case of Cu2Se, a peculiar band conductor which shows anomalies in the Hall measurement of the high temperature phase and also in other transport properties at the phase transition, the transport function approach is applied as a workaround for modeling. On the practical side, for thermoelectric applications, the transport function approach is used to characterize material quality factors for both majority carrier conduction and bipolar conduction. Finally, experimental efforts for improving the accuracy and applicability of Seebeck measurements is discussed.

The thermoelectric performance of Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01) was improved by reducing the amount of excess Mg (x = 0.01-0.2). A 20% reduction in effective lattice thermal conductivity at 600 K was observed by decreasing the nominal xfrom 0.2 to 0.01 in Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01), leading to a 20% improvement in the figure-of-merit zT. Since materials with different amounts of Mg have similar electronic properties, the enhancement is attributed primarily to the reduction in thermal conductivity. It is known that excess Mg is required to make n-type Mg_(3+x)Sb_(1.5)Bi_(0.49)Te_(0.01); however, too much excess Mg in the material increases the thermal conductivity and is therefore detrimental for the overall thermoelectric performance of the material.

Thermoelectric semiconducting materials are often evaluated by their figure-of-merit, zT. However, by using zT as the metric for showing improvements, it is not immediately clear whether the improvement is from an enhancement of the inherent material property or from optimization of the carrier concentration. Here, we review the quality factor approach which allows one to separate these two contributions even without Hall measurements. We introduce practical methods that can be used without numerical integration. We discuss the underlying effective mass model behind this method and show how it can be further advanced to study complex band structures using the Seebeck effective mass. We thereby dispel the common misconception that the usefulness of effective band models is limited to single parabolic band materials., 5 pages, 3 figures

Exome and targeted sequencing studies have identified potential driver mutations for a variety of tumor types. Cutaneous squamous cell carcinoma (cSCC) is one of the most highly mutated cancers but typically is associated with low rates of metastasis and high survival rates. Nevertheless, metastatic cSCC is a significant health threat; up to 8800 individuals die each year of this disease.Because it is difficult to predict which cSCCs are more likely to metastasize, and because to the best of the authors' knowledge there are no targeted therapies specifically designated for patients with metastatic cSCC, exome and/or targeted sequencing of 18 metastatic and 10 primary cSCCs was performed to identify mutations that were more frequent in metastatic tumors and might be targeted for therapeutic benefit. The authors compared their results with published sequencing results of an additional 223 primary tumors and 68 metastatic cSCCs.The authors identified genes demonstrating higher mutation frequencies in metastatic cSCC compared with primary tumors, including the chromatin remodeling gene lysine methyltransferase 2D (KMT2D) and the classic skin tumor suppressor tumor protein p53 (TP53), which was found to be mutated in 54% of primary tumors compared with 85% of metastatic tumors (P.0001).These studies appear to uncover potential pathways that are important in metastatic cSCC and that broaden understanding of the biology contributing to aggressive tumor behavior. These results may lead to new therapeutic strategies. Cancer 2017;123:1184-1193. © 2016 American Cancer Society.

Intrinsically doped samples of YCuTe2 were prepared by solid state reaction of the elements. Based on the differential scanning calorimetry and the high temperature X-ray diffraction analyses, YCuTe2 exhibits a first order phase transition at ∼440 K from a low-temperature-phase crystallizing in the space group P3m1 to a high-temperature-phase in P3. Above the phase transition temperature, partially ordered Cu atoms become completely disordered in the crystal structure. Small increases to the Cu content are observed to favour the formation of the high temperature phase. We find no indication of superionic Cu ions as for binary copper chalcogenides (e.g., Cu2Se or Cu2Te). All investigated samples exhibit very low thermal conductivities (as low as ∼0.5 W m-1 K-1 at 800 K) due to highly disordered Cu atoms. Electronic structure calculations are employed to better understand the high thermoelectric efficiency for YCuTe2. The maximum thermoelectric figure of merit, zT, is measured to be ∼0.75 at 780 K for Y0.96Cu1.08Te2, which is promising for mid-temperature thermoelectric applications.

The superionic phase transition of Cu2-xSe accompanies drastic changes in transport properties. The Seebeck coefficient increases sharply while the electrical conductivity and thermal diffusivity drops. Such behavior has previously been attributed to critical phenomena under the assumption of a continuous phase transition. However, applying Landau's criteria suggests that the transition should be first order. Using the phase diagram that is consistent with a first order transition, we show that the observed transport properties and heat capacity curves can be accounted for and modeled with good agreement. The apparent critical phenomena is shown to be a result of compositional degree-of-freedom. Understanding of the phase transition allows to explain the enhancement in the thermoelectric figure-of-merit that is accompanied with the transition.

The superionic phase transition of Cu_(2-x)Se accompanies drastic changes in transport properties. The Seebeck coefficient increases sharply while the electrical conductivity and thermal diffusivity drops. Such behavior has previously been attributed to critical phenomena under the assumption of a continuous phase transition. However, applying Landau's criteria suggests that the transition should be first order. Using the phase diagram that is consistent with a first order transition, we show that the observed transport properties and heat capacity curves can be accounted for and modeled with good agreement. The apparent critical phenomena is shown to be a result of compositional degree-of-freedom. Understanding of the phase transition allows to explain the enhancement in the thermoelectric figure-of-merit that is accompanied with the transition.

Current microelectronic packages consist of multilayer systems. Adhesion strength is one of the most important factors to the reliability of these systems. Previous studies have used four point bending tests as a method for characterizing the energy release rate to obtain the adhesion strength of bilayer systems. An extension of this work is proposed in this study, where a four point bending test of multilayer structures with a vertical crack is used to measure the adhesion strength, assisted by the presence of a predefined area. The predefined area allows for a weak adhesion horizontal accurate pre-crack which permits crack propagation under loading as well as reducing scatter within the values of critical loads. A numerical analysis is conducted to compute the energy release rate from the critical loads using the concept of the J-integral. Two sets of multilayer specimens were fabricated and tested in the study: one for investigating crack front behavior relative to the compliance change in the load-displacement profile by using transparent substrates, and the other using the previous set as a guideline for testing metal substrates under certain environmental conditions. Experimental results along with visual evidence support the consistent behavior between crack front behavior and compliance change. This correlation can be used as a baseline for testing other electronic packages for interfacial failure.

Thermoelectric coils for energy harvesting are fabricated in miniature flexible devices., With accelerating trends in miniaturization of semiconductor devices, techniques for energy harvesting become increasingly important, especially in wearable technologies and sensors for the internet of things. Although thermoelectric systems have many attractive attributes in this context, maintaining large temperature differences across the device terminals and achieving low–thermal impedance interfaces to the surrounding environment become increasingly difficult to achieve as the characteristic dimensions decrease. Here, we propose and demonstrate an architectural solution to this problem, where thin-film active materials integrate into compliant, open three-dimensional (3D) forms. This approach not only enables efficient thermal impedance matching but also multiplies the heat flow through the harvester, thereby increasing the efficiencies for power conversion. Interconnected arrays of 3D thermoelectric coils built using microscale ribbons of monocrystalline silicon as the active material demonstrate these concepts. Quantitative measurements and simulations establish the basic operating principles and the key design features. The results suggest a scalable strategy for deploying hard thermoelectric thin-film materials in harvesters that can integrate effectively with soft materials systems, including those of the human body.