Correction to Influence of Generated Defects by Ar Implantation on the Thermoelectric Properties of ScN.

[This corrects the article DOI: 10.1021/acsaem.2c01672.].

Influence of Generated Defects by Ar Implantation on the Thermoelectric Properties of ScN.

Nowadays, making thermoelectric materials more efficient in energy conversion is still a challenge. In this work, to reduce the thermal conductivity and thus improve the overall thermoelectric performances, point and extended defects were generated in epitaxial 111-ScN thin films by implantation using argon ions. The films were investigated by structural, optical, electrical, and thermoelectric characterization methods. The results demonstrated that argon implantation leads to the formation of stable defects (up to 750 K operating temperature). These were identified as interstitial-type defect clusters and argon vacancy complexes. The insertion of these specific defects induces acceptor-type deep levels in the band gap, yielding a reduction in the free-carrier mobility. With a reduced electrical conductivity, the irradiated sample exhibited a higher Seebeck coefficient while maintaining the power factor of the film. The thermal conductivity is strongly reduced from 12 to 3 W·m-1·K-1 at 300 K, showing the influence of defects in increasing phonon scattering. Subsequent high-temperature annealing at 1573 K leads to the progressive evolution of these defects: the initial clusters of interstitials evolved to the benefit of smaller clusters and the formation of bubbles. Thus, the number of free carriers, the resistivity, and the Seebeck coefficient are almost restored but the mobility of the carriers remains low and a 30% drop in thermal conductivity is still effective (k total ∼ 8.5 W·m-1·K-1). This study shows that control defect engineering with defects introduced by irradiation using noble gases in a thermoelectric coating can be an attractive method to enhance the figure of merit of thermoelectric materials.

Real-Time Capturing of Microscale Events Controlling the Sintering of Lead-Free Piezoelectric Potassium-Sodium Niobate.

Sintering is a very important process in materials science and technological applications. Despite breakthroughs in achieving optimized piezoelectric properties, fundamentals of K0.5 Na0.5 NbO3 (KNN) sintering are not yet fully understood, facing densification versus grain growth competition. At present, microscale events during KNN sintering under reducing atmospheres are real-time monitored using a High Temperature-Environmental Scanning Electron Microscope. A two contacting KNN particles model satisfying the Kingery and Berg's bulk diffusion model is reported. Dynamic events like individual grain growth and grain elimination process are explored through a postanalysis of recorded image series. The diffusion coefficient for oxygen vacancies of 10-8 cm2 s-1 and average boundary mobility of 10-9 cm4 J-1 s-1 are reported for the KNN ceramics. Moreover, the local pore shrinkage is consistent with the Kingery and François's concept of pore stability except that pore curvatures are not all concave, convex or flat due to anisotropic grain-boundary energies. The global grain growth kinetics are described using parabolic and/or cubic laws. The effect of atmospheres and microstructure evolution on the intrinsic and extrinsic contributions to the dielectric response using Rayleigh's law is also explored. These results bring a new breath for KNN sintering studies in order to adapt the sintering process.

Modified zeolite-supported biofilm in service of pesticide biodegradation.

The development of biofilms on modified natural zeolites was investigated with purpose to obtain biocomposites with biodegradation activity towards pesticides MCPA (2-methyl-4-chlorophenoxyacetic acid) and glyphosate (N-(phosphonomethyl)glycine) for potential application in bioaugmentation of polluted agricultural soils. Microbial communities were selected from agricultural pesticide-contaminated soil/water samples and enriched on the basis of their ability to biodegrade the pesticides. In order to enhance affinity of microbial communities to the support material, the natural mineral zeolite was modified by nontoxic environmentally friendly cations (Li+, Na+, K+, NH4+, H+, Mg2+, Ca2+, Fe3+) by methods preserving its structure and characterised using powder XRD, surface area measurement and chemical composition analysis. Kinetics of pesticide degradation by the biocomposites was studied in liquid media. Results showed that according to zeolite modifications, the microbial activity and biodiversity changed. The best biodegradation rate of MCPA and glyphosate reached 0.12-0.13 mg/h with half-life of 16-18 h, which is considerably quicker than observed in natural environment. However, in some cases, biodegradation activity towards pesticides was lost which was connected to unfavourable zeolite modification and accumulation of toxic metabolites. High-throughput sequencing on the 16S rRNA genes of the biofilm communities highlighted the selection of bacteria genera known to metabolise MCPA (Aminobacter, Cupriavidus, Novosphingobium, Pseudomonas, Rhodococcus, Sphingobium and Sphingopyxis) and glyphosate (Pseudomonas). Altogether, results suggested that zeolites do not only have a passive role of biofilm support but also have protective and nutrient-supportive functions that consequently increase biodiversity of the pesticide degraders growing in the biofilm and influence the pesticide biodegradation rate.

Reducing the thermal conductivity of La2Mo2O9 with a trivalent praseodymium substitution for its potential use as a thermal barrier coating.

(La1-xPrx)2Mo2O9 powders were synthesized by solid state reaction for x = 0.00, 0.10, 0.25, 0.50, 0.75 and 1.00. Dense pellets were obtained by conventional sintering in air. Their thermal stability and thermal conductivity were measured from 100 to 700 °C and their cell parameters refined from X-ray powder diffraction pattern by the Rietveld method. A 50 mol% isovalent substitution of lanthanum in La2Mo2O9 by praseodymium stabilizes the high temperature ß phase while reducing the thermal conductivity of the parent compound by 11-18%. For a praseodymium content x higher than 0.75, the thermal conductivity increases and a phase transition similar to that of La2Mo2O9 is observed except that the room temperature phase appears to be this time triclinic in symmetry.

Inversion Boundaries and Phonon Scattering in Ga:ZnO Thermoelectric Compounds.

We investigated the high-temperature thermoelectric properties of Ga:ZnO bulk compounds, synthesized using a simple and scalable solid-state process. The effects of a low gallium content (x ≤ 0.04 in Zn1-xGaxO1+x/2) on the structural features and electrical/thermal properties are reviewed. Transmission electron microscopy analyses showed that 2D, nonperiodic defects had formed from a doping content as low as x = 0.01 Ga. The structural description of these nanoscale interfaces is, for the first time, carefully investigated in such low-Ga-content samples by HAADF-STEM analyses combined with structural modeling. It was found that the formation of head-to-head inversion twin (h-IT) boundaries and tail-to tail inversion boundaries (t-IB) in the bulk compounds is responsible for strong phonon scattering, while maintaining relatively good electrical conductivity and thereby enhancing the thermoelectric properties. The absolute value of the Seebeck coefficient decreases abruptly from 475 µV/K for x = 0 down to 60 µV/K for x = 0.005 at 350 K. At the same time, the electrical resistivity drops from 1 ohm cm for x = 0 to 1.7 × 10-3 ohm cm for x = 0.005. For higher Ga additions (x > 0.01), the increase in electrical resistivity is likely linked to the formation of interface defects at a larger extent in the wurtzite structure. The thermal conductivity also drops sharply with the increase in the Ga content from ∼33 W/m K for x = 0 to ∼8 for x = 0.04 at 350 K. This study is progress toward the synthesis of other thermoelectric materials where nanoscale interfaces in bulk compounds provide tremendous opportunities for further enhancing both the phonon scattering and the overall figure of merit.

Ultrasonic transducers based on undoped lead-free (K0.5Na0.5)NbO3 ceramics.

Lead zirconate titanate (PZT) ceramics are the dominant piezoelectric elements for non-destructive evaluation (NDE) and ultrasonic transducers devices. However, the presence of lead content may impose the scientific community to develop lead-free ceramics, concerning human health and environmental safety. During the past ten years, many contributions have highlighted the potential properties of complex compositions like LiNbO3, LiTaO3 and LiSbO3 in the lead-free (K0.5Na0.5)NbO3 KNN system. In this context, for the first time, the practical applications and the effectiveness of simply undoped (K0.5Na0.5)NbO3 (KNN) ceramics are investigated. KNN powder is prepared by conventional solid state mixed oxide route. Ceramics of this material are prepared using conventional sintering (CS) and spark plasma sintering (SPS). Thickness coupling factor kt of 44-46%, planar coupling factor kp of 29-45%, relative permittivity at constant strain ε33,r(S) of 125-243 and acoustic impedance Z of 23-30 MRay are obtained for these two kinds of undoped KNN ceramics. Both ceramics are used to build single-element ultrasonic transducers. Relative bandwidth of 49-78% and insertion loss of -27 and -51dB are obtained for SPS and CS transducers, respectively. These results are suitable for use in non-destructive evaluation. The effectiveness of undoped KNN is evaluated using the KLM model, and compared to standard PZT based probe. Finally, chemical aging test of undoped KNN has demonstrated its stability in water.

La10W2O21: an anion-deficient fluorite-related superstructure with oxide ion conduction.

The crystal structure of La10W2O21, which has to be reformulated (La5.667W0.333)LaWO14□2, is best described, on average, by a 2 × 2 × 2 anion-deficient fluorite-related superstructure cubic cell, with space group F4 3m, Z = 4, and a = 11.17932(6) Å, similar to Y7ReO14--δ. The 32 cations are distributed with lanthanum on the 4a-site, tungsten on the 4b-site, and a partial occupancy of the 24g-site by La (94%) and W. The 56 oxygen atoms occupy four 16e-sites, three of them fully and with an occupancy of 1/2 for the fourth one. Others M10W2O21 (M = Er, Y) adopt a 3 × 2 × 2 fluorite superstructure with W in octahedral sites, whereas W is mainly in tetrahedral sites in La10W2O21. Several powerful techniques such as crystal image furnace synthesis, (139)La nuclear magnetic resonance (NMR) and convergent beam electron diffraction (CBED) were used to achieve our results. Transmission electron microscopy (microdiffraction, CBED, and Tanaka patterns) brought us the real symmetry, showing that indeed classical cubic twinning along the 3-fold axis does take place. The surprising La/W mixed site is nicely confirmed by (139)La NMR. This compound exhibits interesting fast oxide ion conducting properties, comparable with LAMOX (Lacorre et al. Nature 2000, 404, 856-858) at low temperature. As opposed to many ionic conductors, no temperature structural transition is observed. Its conductivity is about 6.4 × 10(-4) S·cm(-1) at 700 °C.