Introduction Of Point Defects Research Articles

Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in FeCoNi/FeAl2O4 hybrid coatings, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High‐Performance Electrocatalysts

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in FeCoNi/FeAl2O4 hybrid coatings, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm−2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect‐engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Enhanced photoelectrochemical water splitting via hydrogenated TiO2 nanotubes modified with Cu/CuO species

This study explores the collective influence of hydrogenation thermal treatment and the decoration of Cu/CuO onto TiO2 nanotubes (TiO2-NTs) concerning photoelectrochemical water splitting. To introduce point defects such as oxygen vacancies and Ti3+, electrochemically anodized Ti foils underwent hydrogenation in a 90 % Ar-10 % H2 atmosphere at 500 °C. Subsequently, Cu/CuO species were deposited on the hydrogenated TiO2-NTs through chemical decoration for varying stirring durations of 15, 30, 45, and 60 min. EPR analysis of the hydrogenated sample unveiled resonances at g-values distinct from the typical 1.997 signal associated with oxygen vacancies in TiO2-NTs, signifying the presence of Ti3+ and VO defects. Analysis via XPS identified Cu and CuO as the primary compositions of the decorated species on the hydrogenated TiO2-NTs. Additionally, SEM/EDS results showcased that longer stirring times, specifically 60 min., caused localized agglomeration of Cu/CuO species and TiO2-NTs breakage. The Cu/CuO-decorated hydrogenated TiO2-NTs exhibited enhanced absorption of visible light, leading to a band gap reduction to 2.09 eV after 45 min of Cu/CuO decoration. Notably, this particular sample demonstrated the highest photocurrent of 3.6 mA/cm2 and a photo-conversion efficiency of 2.48 % at 1.23 V vs. RHE. Overall, the presence of Cu/CuO species prolonged the lifetime of charge carriers, as evidenced by Nyquist plots and Mott-Schottky analysis. A schematic model is suggested based on the modified band gap of hydrogenated TiO2-NTs subsequent to Cu/CuO loading.

Study on the Effect of Sn, In, and Se Co-Doping on the Thermoelectric Properties of GeTe.

GeTe and Ge0.99-xIn0.01SnxTe0.94Se0.06 (x = 0, 0.01, 0.03, and 0.06) samples were prepared by vacuum synthesis combined with spark plasma sintering (SPS). The thermoelectric properties of GeTe were coordinated by multiple doping of Sn, In, and Se. In this work, a maximum zT(zT = S2σT/κ) of 0.9 and a power factor (PF = S2σ) of 3.87 μWmm-1 K-2 were obtained in a sample of Ge0.99In0.01Te0.94Se0.06 at 723K. The XRD results at room temperature show that all samples are rhombohedral phase structures. There is a peak (~27°) of the Ge element in GeTe and the sample (x = 0), but it disappears after Sn doping, indicating that Sn doping can promote the dissolution of Ge. The scattering mechanism of the doped samples was calculated by the conductivity ratio method. The results show that phonon scattering Is dominant in all samples, and alloy scattering is enhanced with the increase in the Sn doping amount. In doping can introduce resonance energy levels and increase the Seebeck coefficient, and Se doping can introduce point defects to suppress phonon transmission and reduce lattice thermal conductivity. Therefore, the thermoelectric properties of samples with x = 0 improved. Although Sn doping will promote the dissolution of Ge precipitation, the phase transition of the samples near 580 K deteriorates the thermoelectric properties. The thermoelectric properties of Sn-doped samples improved only at room temperature to ~580 K compared with pure GeTe. The synergistic effect of multi-element doping is a comprehensive reflection of the interaction between elements rather than the sum of all the effects of single-element doping.

The effect of iron ion irradiation on the ionic conductivity of lithium lanthanum zirconium oxide garnet thin films

The ionic conductivity of most lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12) solid electrolytes requires improvement. In this study, LLZO thin films were fabricated through sputtering, and various doses of iron ion irradiation (Fe11+) were employed. As the irradiation dose increased from 1014 ions cm−2 to 1016 ions cm−2, the half-height width of the X-ray diffraction peak gradually broadened. Concurrently, the ionic conductivity increased from 2.3 × 10−9 S cm−1 to 2.4 × 10−5 S cm−1, while the activation energy decreased from 0.37 eV to 0.18 eV. The improved ionic conductivity can be attributed to the introduction of point defects in the microstructure of the LLZO thin film upon irradiation. Overall, the findings demonstrate the effective enhancement of the ionic conductivity of LLZO solid electrolytes through iron ion irradiation.

Mechanical properties of defective kaolinite in tension and compression: A molecular dynamics study

Influenced by the external environment, clays often contain a large number of lattice defects inside, and the defects have an essential influence on the physical and mechanical properties of clays. In order to reveal the mechanical properties and deformation failure mechanism of defective kaolinite, kaolinite containing Si vacancy defects was constructed, and the mechanical properties of two types of perfect/defective kaolinite were investigated under uniaxial tensile and compressive conditions, respectively, by using molecular dynamics methods. The anisotropy of the micromechanical behavior of kaolinite and the formation mechanism was revealed. Based on the radial distribution function between atoms, the cutoff distance of individual bonds inside the crystal was determined, and the evolution rules of individual bonds inside the crystal during the deformation and destruction were elucidated. Results showed that the introduction of point defects caused different degrees of reduction in the peak strength and elastic modulus of kaolinite, and the decrease was related to the loading direction, and the decline was more significant for parallel clay layers (x- and y-) than for perpendicular clay layers (z-), with pronounced anisotropy. When the defected kaolinite was extended along the x- and y-directions, the silicon‑oxygen tetrahedral and aluminum‑oxygen octahedral sheets were fractured, and the broken sites were concentrated at the defected locations; when extended along the z-direction, the failure was dominated by the fracture of interlayer hydrogen bonds. When the defective kaolinite was compressed along the x- and y-directions, the failure was mainly caused by the gradual accumulation of the bending of the clay layer, which was distinctly different from the direct fracture under the tensile condition, and when compressed along the z-direction, the clay layer collapsed until it was failure. The tendency of the broken bonds within kaolinite corresponded well with the stress-strain curve, the number of broken bonds increased with the increase of strain, and the number of broken bonds of various bonds stabilized when the crystal structure was destroyed. The bond-break types and the number of bonds broken under different simulation conditions were somewhat different, affected by the layered structure of kaolinite and the loading patterns.

Investigation of the Impact of Point Defects in InGaN/GaN Quantum Wells with High Dislocation Densities.

In this work, we report on the efficiency of single InGaN/GaN quantum wells (QWs) grown on thin (<1 µm) GaN buffer layers on silicon (111) substrates exhibiting very high threading dislocation (TD) densities. Despite this high defect density, we show that QW emission efficiency significantly increases upon the insertion of an In-containing underlayer, whose role is to prevent the introduction of point defects during the growth of InGaN QWs. Hence, we demonstrate that point defects play a key role in limiting InGaN QW efficiency, even in samples where their density (2-3 × 109 cm-2) is much lower than that of TD (2-3 × 1010 cm-2). Time-resolved photoluminescence and cathodoluminescence studies confirm the prevalence of point defects over TDs in QW efficiency. Interestingly, TD terminations lead to the formation of independent domains for carriers, thanks to V-pits and step bunching phenomena.

Effect of sub-micron grains and defect-dipole interactions on dielectric properties of iron, cobalt, and copper doped barium titanate ceramics.

Introduction: Dilutely doped ferroelectric materials are of interest, as engineering these materials by introducing point defects via doping often leads to unique behavior not otherwise achievable in the undoped material. For example, B-site doping with transition metals in barium titanate (BaTiO3, or BTO) creates defect dipoles via oxygen vacancies leading enhanced polarization, strain, and the ability to tune dielectric properties. Though defect dipoles should lead to dielectric property enhancements, the effect of grain size in polycrystalline ferroelectrics such as BTO plays a significant role in those properties as well. Methods: Herein, doped BTO with 1.0% copper (Cu), iron (Fe), or cobalt (Co) was synthesized using traditional solid-state processing to observe the contribution of both defect-dipole formation and grain size on the ferroelectric and dielectric properties. Results and discussion: 1.0% Cu doped BTO showed the highest polarization and strain (9.3μC/cm2 and 0.1%, respectively) of the three doped BTO samples. While some results, such as the aforementioned electrical properties of the 1.0% Cu doped BTO can be explained by the strong chemical driving force of the Cu atoms to form defect dipoles with oxygen vacancies and copper's consistent +2 valency leading to stable defect-dipole formation (versus the readily mixed valency states of Fe and Co at +2/+3), other properties cannot. For instance, all three Tc values should fall below that of undoped BTO (typically 120°C-135°C), but the Tc of 1.0% Cu BTO actually exceeds that range (139.4°C). Data presented on the average grain size and distribution of grain sizes provides insight allowing us to decouple the effect of defect dipoles and the effect of grain size on properties such as Tc, where the 1.0% Cu BTO was shown to possess the largest overall grains, leading to its increase in Tc. Conclusion/future work: Overall, the 1% Cu BTO possessed the highest polarization, strain, and Tc and is a promising dopant for engineering the performance of the material. This work emphasizes the challenge of extricating one effect (such as defect-dipole formation) from another (grain size modification) inherent to doping polycrystalline BTO.

Rejuvenation of giant electrostrain in doped barium titanate single crystals

Engineering materials through the introduction of point defects has resulted in significant advances in semiconductor processing and, more recently, the observation of novel phenomena such as large reconfigurable strains in ferroelectrics as a result of defect dipole complexes. Up to 0.8% strain has been demonstrated in BaTiO3 crystals dilutely doped with iron. However, the defect dipole pinning sites and the corresponding achievable strains are found to degrade as the crystal is electrically cycled as part of the measurement process. The strain degradation rate is dependent on the applied field values but shows an exponential change in materials properties regardless of the electric field. This behavior, plus a change in impedance with number of times cycled, suggests these changes are due to electric field induced oxygen migration—similar to the cause of the resistance degradation effect. Despite this, effective piezoelectric coefficients of over 4700 pm/V were recorded with 1.5 kV/cm fields, one of the largest values for a lead-free piezoelectric material thus far. In addition, the defect dipole-aligned state and the high strains can be repeatably recovered by a subsequent heat treatment step after cycling. Potential paths to exploiting the defect dipole induced effects and large piezoelectric coefficient in these dilutely doped systems are proposed.

Defect-Engineering of 2D Dichalcogenide VSe2 to Enhance Ammonia Sensing: Acumens from DFT Calculations

Opportune sensing of ammonia (NH3) gas is industrially important for avoiding hazards. With the advent of nanostructured 2D materials, it is felt vital to miniaturize the detector architecture so as to attain more and more efficacy with simultaneous cost reduction. Adaptation of layered transition metal dichalcogenide as the host may be a potential answer to such challenges. The current study presents a theoretical in-depth analysis regarding improvement in efficient detection of NH3 using layered vanadium di-selenide (VSe2) with the introduction of point defects. The poor affinity between VSe2 and NH3 forbids the use of the former in the nano-sensing device's fabrications. The adsorption and electronic properties of VSe2 nanomaterials can be tuned with defect induction, which would modulate the sensing properties. The introduction of Se vacancy to pristine VSe2 was found to cause about an eight-fold increase (from -012 eV to -0.97 eV) in adsorption energy. A charge transfer from the N 2p orbital of NH3 to the V 3d orbital of VSe2 has been observed to cause appreciable NH3 detection by VSe2. In addition to that, the stability of the best-defected system has been confirmed through molecular dynamics simulation, and the possibility of repeated usability has been analyzed for calculating recovery time. Our theoretical results clearly indicate that Se-vacant layered VSe2 can be an efficient NH3 sensor if practically produced in the future. The presented results will thus potentially be useful for experimentalists in designing and developing VSe2-based NH3 sensors.

Approaches to Estimate the Magnitude of Phonon Scattering via Point Defects in Mo(Se1-xTex)2 Thermoelectric Alloys

One of the most popular routes used to improve the thermoelectric performance of materials is to suppress their lattice thermal conductivities. Thermoelectric performance is characterized by a figure-of-merit &lt;i&gt;zT&lt;/i&gt;, which is defined as &lt;i&gt;σS&lt;sup&gt;2&lt;/sup&gt;T&lt;/i&gt;/(&lt;i&gt;κe&lt;/i&gt; + &lt;i&gt;κl&lt;/i&gt;), where the &lt;i&gt;σ&lt;/i&gt;, &lt;i&gt;S&lt;/i&gt;, &lt;i&gt;T&lt;/i&gt;, &lt;i&gt;κe&lt;/i&gt;, and &lt;i&gt;κl&lt;/i&gt; are the electrical conductivity, Seebeck coefficient, temperature (in Kelvin), electronic thermal conductivity, and the lattice thermal conductivity, respectively. Among the variables in &lt;i&gt;zT&lt;/i&gt;, the &lt;i&gt;κl&lt;/i&gt; is the only variable that is independent of all other variables. In other words, reduction in &lt;i&gt;κl&lt;/i&gt; guarantees &lt;i&gt;zT&lt;/i&gt; improvement. Therefore, several different strategies to decrease &lt;i&gt;κl&lt;/i&gt; have been introduced and implemented. Among the many &lt;i&gt;κl&lt;/i&gt; reduction strategies, introducing point defects in the material by forming an alloy is particularly effective. Here, phonon scattering due to point defects in Mo(Se1-xTex)2 (&lt;i&gt;x&lt;/i&gt; = 0.0, 0.25, 0.50, 0.75, 1.0) was studied using both the Debye-Callaway (DC) model and Callaway-von Baeyer (CvB) model. The advantages and disadvantages of using DC or CvB models are thoroughly discussed. When analyzing the effect of phonon scattering due to point defects, the CvB model is simpler and gives more information about the details of phonon scattering.

Enhanced Thermoelectric Performance and Mechanical Property in Layered Chalcostibite CuSb1–xPbxSe2

In this work, the thermoelectric properties of p-type layered chalcostibite CuSb1–xPbxSe2 (x = 0–0.10) compounds prepared by vacuum melting reaction and uniaxial hot press, have been studied in the temperature range of 323–623 K. Further, aliovalent Pb2+ doping at Sb3+ site in CuSbSe2 notably increases the hole concentration due to its acceptor nature and thereby enhances the electrical conductivity, σ. Importantly, a huge reduction in total thermal conductivity, κtotal has been noticed, from ∼1.7 W/mK (pristine CuSbSe2) to ∼0.72 W/mK at 323 K for CuSb0.90Pb0.10Se2 owing to increased phonon scattering from the introduced point defects and mass-difference between Pb and Sb. As a result, the thermoelectric figure of merit, zT, has been enhanced to ∼0.27 at 623 K for the composition of CuSb0.90Pb0.10Se2, which is 3-fold higher than that of the undoped CuSbSe2. Further, the hardness value achieved was ∼125.54 Hv, which is significantly higher than the most of the state-of-the-art materials, indicating it to be an efficient thermoelectric material for intermediate temperature.

The effects of point defects on thermal-mechanical properties of BiCuOTe: a first-principles study.

Recently, BiCuOTe as a promising thermoelectric material has attracted extensive interest due to its lower thermal conductivity and higher electrical conductivity. However, little is known about the role of point defects in the growth, processing, and device degradation of this material. Moreover, the elastic properties which provide valuable information about the bonding characteristics, heat conductivity, and their anisotropic characters are investigated for effective design and characterization of new devices. Motivated by these considerations, a first-principles study about the stability of point defects and their effects on the thermal-mechanical properties of BiCuOTe was performed. The vacancies are found to be more stable than the interstitials. XO (here X occupying the O lattice site, with X = Cu, Bi or Te) are generally unfavorable among the considered point defects. Point defects generally have negative effects on elastic constants (except C66), suggesting that the resistance of defective systems to uniaxial and shear deformation is usually weaker than the that of ideal BiCuOTe. Similarly, point defects could deteriorate the ability to resist external compression. However, the introduction of point defects may improve the elastic compliances and depress the Debye temperature, which may increase the thermal expansion efficient of BiCuOTe. As compared with the ideal system, the point defects such as CuBi, TeBi, BiTe, OCu, CuTe and TeCu may generally reduce the phonon thermal conductivity. This study would provide insights into the effect of point defects on the elastic and thermal properties of BiCuOTe and has important implications in the rational design of superior thermoelectric materials.

Defect-Engineered Cu-Based Nanomaterials for Efficient CO2 Reduction over Ultrawide Potential Window

High conversion efficiency over a wide operating potential window is important for the practical application of CO2 reduction electrocatalysis, yet that remains a huge challenge in differentiating the competing CO2 reduction and H2 evolution. Here we introduce point defects (Sn doping) and planar defects (grain boundary) into the Cu substrate. This multidimensional defect integration strategy guides the fabrication of highly diluted SnCu polycrystal, which exhibits high Faradaic efficiencies (>95%) toward CO2 electroreduction over an ultrawide potential window (ΔE = 1.3 V). The theoretical study indicates that the introduction of Sn doping and grain boundary synergistically provides an optimized electronic effect, which helps suppress H2 evolution and promotes the hydrogenation of *CO2.

Gesn Bonding Technology for Integrated Laser-on-Chip Photonics

With the numerous recent demonstrations of germanium-tin (GeSn) semiconductor lasers, this material has become the strongest candidate for the realization of photonic-integrated circuits (PICs). However, the high defect density of this material often results in high lasing thresholds, making them undesirable for real-world applications. Furthermore, the low-thermal budget of high Sn content (>9 at.%) GeSn makes it exceptionally hard to grow onto other materials without introducing point defects. Herein, we present a novel method of directly combining GeSn with other materials through low-temperature wafer bonding. Through this technique, we can reduce the harmful high defect density and improve the lasing performance. To cater to the low thermal budget, we optimized the bonding processes which is critical in preventing Sn segregation to the surface. Through this method, we provide compelling evidence for the enhancement in photoluminescence in GeSn. Additionally, this technique can be extended to fabricate new material stacks, presenting unforeseen opportunities in other fields such as non-linear photonics.

Realizing High Thermoelectric Performance of Ag/Al Co‐Doped Polycrystalline SnSe through Band Structure Modification and Hydrogen Reduction

AbstractSingle crystal tin selenide (SnSe) has a recorded high thermoelectric figure of merit (ZT) value of 2.6 at 923 K, but it is easy to form mechanical cracks and difficult to apply in thermoelectric conversion devices. Polycrystalline SnSe has better mechanical properties but inferior ZT values, which needs further optimization for applications. This work aims at enhancing the thermoelectric performance of polycrystalline SnSe through synergistic optimization of sliver (Ag) and aluminum (Al) co‐doping with the hydrogen reduction. The effects of Ag and Al doping on electronic transport properties are systematically investigated by density functional theory calculation and experimental measurement. Compared with pristine SnSe, Ag doping can effectively increase the hole concentration to 1.58 × 1019 cm−3 and improve the conductivity. Results also indicate that using Al dopant may slightly decrease the hole concentration but reduce the thermal excitation temperature, and introduce point defects reducing the lattice thermal conductivity through scattering phonons. In addition, the hydrogen reduction of sample powders before synthesis can effectively remove Sn oxides and reduce lattice thermal conductivity. At last, a state‐of‐the‐art maximum ZT value of 1.69 at 823 K is obtained in Ag0.01Al0.01Sn0.98Se. This study provides a theoretical basis and technical guidance for designing high‐performance polycrystalline SnSe.

Failure modes and mechanisms of layered h-BN under local energy injection

Layered h-BN may serve as an important dielectric and thermal management material in the next-generation nanoelectronics, in which its interactions with electron beam play an important role in device performance and reliability. Previous studies report variations in the failure strength and mode. In this study, using molecular dynamics simulations, we study the effect of local heat injection due to the electron beam and h-BN interaction on the failure start time and failure mode. It is found that at the same heat injection rate, the failure start time decreases with the increase in the layer number. With the introduction of point defects in the heating zone, the failure always starts from the defect site, and the start time can be significantly shortened. For monolayer h-BN, failure always starts within the layer, and once failure starts, its propagation is through melting or vaporization of the h-BN atoms, and no swelling occurs. For multiple layers, once failure starts within the h-BN film, swelling occurs first. With continued heating, the large pressure induced by melting and vaporization can cause the burst of the layers above, leading to the formation of a pit. In the presence of multiple defects within the heating zone, these defects can interact, causing a further reduction in the failure start time. We also reveal the relation of beam power with layer-by-layer failure mode and swelling/pit formation mode. The present work not only reproduces many interesting experimental observations, but also reveal several interesting mechanisms responsible for the failure processes and modes. It is expected that the findings revealed here may provide useful references for the design and engineering of h-BN for device applications.

Band Modulation and Strain Fluctuation for Realizing High Average zT in GeTe

AbstractRecently, GeTe has emerged as a very promising thermoelectric material. However, the pristine GeTe exhibits intrinsically low Seebeck coefficient and high thermal conductivity. Therefore, resolving these issues is critical for further promoting its thermoelectric performance. Herein, PbTe and AgSbTe2 are chosen to form a solid solution with GeTe. Benefitting from the converged electronic bands and reduced thermal conductivity after AgSbTe2 alloying, the thermoelectric performance of GeTe‐based materials is effectively improved. In addition, PbTe alloying can optimize the carrier concentration and further improve the effective mass, and thus a remarkable enhancement in the Seebeck coefficient is realized. Moreover, intense phonon scattering occurs due to the introduced point defects at the Ge site, and the lattice thermal conductivity is effectively reduced to be as low as ≈0.47 W m−1 K−1. As a result, a high zT of ≈0.7 at 323 K and ≈2.4 at 723 K can be achieved in (Pb0.15Ge0.85Te)0.8(AgSbTe2)0.2, leading to a record‐high average zT of ≈1.8 and a high conversion efficiency of ≈14.8% under the temperature difference of 500 K.

Enhanced Thermoelectric Performance in SmMg2Bi2 via Ca-Alloying and Ge-Doping

Zintl phase compounds with a CaAl2Si2 structure are promising thermoelectric materials. In this paper, enhanced thermoelectric performance was achieved in SmMg2Bi2, a new member of AB2X2 compounds, via Ca-alloying and Ge-doping. The introduction of point defects by alloying Ca on the Sm site significantly reduces the lattice thermal conductivity, and the lowest value was achieved when the Sm/Ca molar ratio is 1:1. Doping Ge on the Bi site increases the hole concentration of the material, which successfully suppresses the bipolar effect and significantly improves the power factor (PF) in the whole temperature range. Due to the decrease of thermal conductivity and the increase of PF over 323–873 K, the peak zT value of Sm0.5Ca0.5Mg2.15Bi1.99Ge0.01 reached 0.71 at 873 K and the zTave approached 0.44, about 51 and 47% enhancement compared with the pristine sample, respectively. This work provides a thermoelectric performance optimization strategy that can be used for other AB2X2 compounds.

Improved Thermal Stability and Enhanced Thermoelectric Properties of p-Type BaCu2Te2 by Doping of Cl.

Doping in semiconductors is a widely implemented strategy for manipulation of carrier concentration, which is a critical parameter to regulate the thermoelectric performance. Stoichiometric BaCu2Te2 shows high hole concentration and unstable transport properties owing to the inherent Cu vacancy and dynamic precipitation behavior. In this work, Te has been partially substituted by Cl in BaCu2Te2 to suppress the overhigh hole concentration. Due to the high electronegativity of Cl, strong Cl-Cu bonds can significantly inhibit the Cu migration and the consequent dynamic precipitation. Meanwhile, nano-precipitate BaCl2 distributes in the grain boundary, acting as ionic blocking layers. Therefore, the thermal stability of the samples can be essentially improved via chemical bonding strengthening and grain boundary engineering. In terms of thermal transport, the introduced point defects and second phase strengthen the short-wavelength and medium-wavelength phonon scattering, leading to further reduced thermal conductivity. Eventually, the repeatable ZT value of BaCu2Te1.98Cl0.02 reached 1.22 at 823 K, which is higher by 19.6% compared with 1.02 of pristine BaCu2Te2. The average ZTs of BaCu2Te2-xClx (x = 0, 0.02, 0.04, and 0.06) in the temperature range of 323-823 K are 0.737 for x = 0.02, 0.689 for x = 0.04, and 0.667 for x = 0.06, which are 24.6, 17.2, and 13.4% higher than the average ZT of 0.588 corresponding to the undoped sample, respectively. The study shows that synergetic enhancements of thermal stability and thermoelectric properties can be achieved by strengthening chemical bonding and constructing ionic blocking layers in the grain boundary, which can be applied to other fast-ionic conductor thermoelectric materials.