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We report on atom probe tomography studies of the composition at internal interfaces in Cu2ZnSnSe4 thin-films. For Cu2ZnSnSe4 precursors, which are deposited at 320 °C under Zn-rich conditions, grain boundaries are found to be enriched with Cu irrespective of whether Cu-poor or Cu-rich growth conditions are chosen. Cu2ZnSnSe4 grains are found to be Cu-poor and excess Cu atoms are found to be accumulated at grain boundaries. In addition, nanometer-sized ZnSe grains are detected at or near grain boundaries. The compositions at grain boundaries show different trends after annealing at 500 °C. Grain boundaries in the annealed absorber films, which are free of impurities, are Cu-, Sn-, and Se-depleted and Zn-enriched. This is attributed to dissolution of ZnSe at the Cu-enriched grain boundaries during annealing. Furthermore, some of the grain boundaries of the absorbers are enriched with Na and K atoms, stemming from the soda-lime glass substrate. Such grain boundaries show no or only small changes in composition of the matrix elements. Na and K impurities are also partly segregated at some of the Cu2ZnSnSe4/ZnSe interfaces in the absorber, whereas for the precursors, only Na was detected at such phase boundaries possibly due to a higher diffusivity of Na compared to K. Possible effects of the detected compositional fluctuations on cell performance are discussed. [ABSTRACT FROM AUTHOR]

Thin-film solar cells based on Cu(In,Ga)Se2 (CIGSe) reach high power-conversion efficiencies in spite of large dislocation densities of up to 1010–1011 cm–2. The present work gives insight into the structural and compositional properties of dislocations in CIGSe thin films, which are embedded in a complete solar cell stack. These properties are related to the average electrical potential distributions obtained by means of inline electron holography. At a part of the dislocations studied, the average electrostatic potential shows local minima, all with depths of about –1.4V. The measured average electrostatic potential distributions were modeled in order to reveal possible influences from strain fields, excess charge, and also compositional changes at the dislocation core. Cu depletion around the dislocation core, as evidenced by atom-probe tomography, explains best the measured potential wells. Their influences of the strain field around the dislocation core and of excess charge at the dislocation core are small. A structural model of dislocations in CIGSe thin films is provided which includes a Cu-depleted region around the dislocation core and gives a possible explanation for why decent photovoltaic performances are possible in the presence of rather large dislocation densities. [ABSTRACT FROM AUTHOR]

The redistribution of boron during the formation of the Ni silicides was investigated using atom probe tomography and transmission electron microscopy. A 7 nm amorphous intermixed region was found after deposition of a 30 nm thick Ni film at room temperature. The formation of this Ni–Si layer was found to have almost no influence on the boron implantation profile. After heating at 290 °C for 1 h, three types of silicides (Ni2Si, NiSi, and NiSi2) were identified below a thin remaining film of Ni (8 nm). The unexpected presence of the silicon-rich NiSi2 phase at this temperature may be caused by the presence of a thin silicon oxide (SiO2) observed at the Ni/Ni2Si interface that may act as a diffusion barrier. The average boron profile in NiSi2 and NiSi silicides is similar to the profile in the silicon substrate before reaction. A segregation of boron at several interfaces was detected. Small boron clusters (1.5 at. %) were found in NiSi, NiSi2, and Si phases but not in Ni2Si. After a 1 min heat treatment at 450 °C, the NiSi phase is the only silicide present. Boron clusters with a platelet shape and a concentration of 3 to 5 at. % of boron were found in both NiSi and Si. The presence of boron in the Ni silicide and its precipitation in the form of tiny clusters is likely to affect the electrical properties of the contacts. [ABSTRACT FROM AUTHOR]

Laser-assisted wide angle tomographic atom probe was employed to investigate clustering of boron in highly doped implanted silicon (11B, 10 keV, 5×1015 atoms/cm2) at room temperature and at different annealing temperatures (600 °C/h, 800 °C/h, and 900 °C/5 h). The implantation profile shows a maximum of 1021 atoms/cm3 at a distance close to 30 nm. The evolution of microstructural features (cluster and matrix composition, cluster size, molar fraction of clusters, and density) was studied as a function of depth. As expected, the number density of clusters shows a maximum (2×1018 and 1.7×1018 cm-3 for 600 and 800 °C, respectively) at the implantation peak where the driving force for nucleation is the highest. As expected, the overall number density of clusters decreases when increasing temperature (lower supersaturation). The boron concentration in clusters as well as that in the parent boron-depleted phase was found to follow the same trend as the implantation profile. The boron level in clusters was found higher close to the implantation peak (8.9 at. % at 600 °C, 12 at. % at 800 °C). The increasing concentration of boron in clusters as a function of temperature suggests the clusters are metastable nuclei of a transient phase, the composition approaches that of equilibrium borides as given by phase diagram (SiB3). This equilibrium boride SiB3 is detected after a heat treatment at 900 °C for 5 h. Experiments were confronted to predictions as given by classical nucleation theory. Reasonable agreement was observed. [ABSTRACT FROM AUTHOR]

Grain boundaries in materials have substantial influences on device properties, for instance on mechanical stability or electronic minority carrier lifetime in multicrystalline silicon solar cells. This applies especially to asymmetric, less ordered or faceted interface portions. Here, we present the complex atomic interface structure of an asymmetric Σ9 tilt grain boundary in silicon, observed by high resolution scanning transmission electron microscopy (HR-STEM) and explained by atomistic modeling and computer simulation. Structural optimization of interface models for the asymmetric Σ9 and related symmetrical Σ9 and Σ3 tilt grain boundaries, by means of molecular-statics simulations with empirical silicon potentials in combination with first-principles calculations, results in a faceted asymmetric interface structure, whose grain-boundary energy is so low that it is likely to exist. The simulated local atomic structures match the observed HR-STEM images very well. [ABSTRACT FROM AUTHOR]

Abstract: Atom Probe Tomography was employed to investigate the distribution of impurities, in particular sodium and oxygen, in a CuInSe2-based thin-film solar cell. It could be shown that sodium, oxygen, and silicon diffuse from the soda lime glass substrate into the CuInSe2 film and accumulate at the grain boundaries. Highly dilute concentrations of sodium and oxygen were measured in the bulk. Selenium was found to be depleted at the grain boundaries. These observations could be confirmed by complementary energy dispersive X-ray spectroscopy studies. Our results support the model proposed by Kronik et al. (1998) , which explains the enhanced photovoltaic efficiency of sodium containing CuInSe2 solar cells by the passivation of selenium vacancies at grain boundaries. [Copyright &y& Elsevier]

Elemental mixing at the CdS/CuInSe2 interface of a thin-film solar cell was studied by means of atom probe tomography. A Cu-depleted and Cd-doped region (∼2 nm in width) was detected at the CuInSe2 surface, proving the existence of a buried p-n homojunction within the CuInSe2 absorber layer. Furthermore, CdS was found to infiltrate open pores existing in CuInSe2 during the chemical bath deposition. This could explain why chemical bath deposition of CdS leads to higher solar cell efficiencies compared to physical vapor deposition of CdS. [ABSTRACT FROM AUTHOR]

Atom probe tomography is frequently employed to characterize the elemental distribution in solids with atomic resolution. Here the potential of this technique to locally probe chemical bonds is reviewed and discussed. Two processes characterize the bond rupture in laser-assisted field emission, the probability of molecular ions (PMI), i.e., the probability that molecular ions are evaporated instead of single (atomic) ions, and the probability of multiple events (PME), i.e., the correlated field-evaporation of more than a single fragment upon laser- or voltage pulse excitation. Here it is demonstrated that one can clearly distinguish solids with metallic, covalent, and metavalent bonds based on their bond rupture, i.e., their PME and PMI values. These findings open new avenues in understanding and designing advanced materials, since they allow a quantification of bonds in solids on a nanometer scale, as will be shown for several examples. These possibilities would even justify calling the present approach bonding probe tomography (BPT)., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Elemental Te is important for semiconductor applications including thermoelectric energy conversion. Introducing dopants such as As, Sb, and Bi has been proven critical for improving its thermoelectric performance. However, the remarkably low solubility of these elements in Te raises questions about the mechanism with which these dopants can improve the thermoelectric properties. Indeed, these dopants overwhelmingly form precipitates rather than dissolve in the Te lattice. To distinguish the role of doping and precipitation on the properties, we have developed a correlative method to locally determine the structure-property relationship for an individual matrix or precipitate. We reveal that the conspicuous enhancement of electrical conductivity and power factor of bulk Te stems from the dopant-induced metavalently bonded telluride precipitates. These precipitates form electrically beneficial interfaces with the Te matrix. A quantum-mechanical-derived map uncovers more candidates for advancing Te thermoelectrics. This unconventional doping scenario adds another recipe to the design options for thermoelectrics and opens interesting pathways for microstructure design., (© 2024. The Author(s).)

Doping is usually the first step to tailor thermoelectrics. It enables precise control of the charge-carrier concentration and concomitant transport properties. Doping should also turn GeSe, which features an intrinsically a low carrier concentration, into a competitive thermoelectric. Yet, elemental doping fails to improve the carrier concentration. In contrast, alloying with Ag-V-VI 2 compounds causes a remarkable enhancement of thermoelectric performance. This advance is closely related to a transition in the bonding mechanism, as evidenced by sudden changes in the optical dielectric constant ε ∞ , the Born effective charge, the maximum of the optical absorption ε 2 (ω), and the bond-breaking behavior. These property changes are indicative of the formation of metavalent bonding (MVB), leading to an octahedral-like atomic arrangement. MVB is accompanied by a thermoelectric-favorable band structure featuring anisotropic bands with small effective masses and a large degeneracy. A quantum-mechanical map, which distinguishes different types of chemical bonding, reveals that orthorhombic GeSe employs covalent bonding, while rhombohedral and cubic GeSe utilize MVB. The transition from covalent to MVB goes along with a pronounced improvement in thermoelectric performance. The failure or success of different dopants can be explained by this concept, which redefines doping rules and provides a "treasure map" to tailor p-bonded chalcogenides., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Grain boundaries (GBs) play a significant role in controlling the transport of mass, heat and charge. To unravel the mechanisms underpinning the charge carrier scattering at GBs, correlative microscopy combined with local transport measurements is realized. For the PbTe material, the strength of carrier scattering at GBs depends on its misorientation angle. A concomitant change in the barrier height is observed, significantly increasing from low- to high-angle GBs. Atom probe tomography measurements reveal a disruption of metavalent bonding (MVB) at the dislocation cores of low-angle GBs, as evidenced by the abrupt change in bond-rupture behavior. In contrast, MVB is completely destroyed at high-angle GBs, presumably due to the increased Peierls distortion. The collapse of MVB is accompanied by a breakdown of the dielectric screening, which explains the enlarged GB barrier height. These findings correlate charge carrier scattering with bonding locally, promising new avenues for the design of advanced functional materials., (© 2023. The Author(s).)

Growth of Cu(In,Ga)Se 2 (CIGS) absorbers under Cu-poor conditions gives rise to incorporation of numerous defects into the bulk, whereas the same absorber grown under Cu-rich conditions leads to a stoichiometric bulk with minimum defects. This suggests that CIGS absorbers grown under Cu-rich conditions are more suitable for solar cell applications. However, the CIGS solar cell devices with record efficiencies have all been fabricated under Cu-poor conditions, despite the expectations. Therefore, in the present work, both Cu-poor and Cu-rich CIGS cells are investigated, and the superior properties of the internal interfaces of the Cu-poor CIGS cells, such as the p-n junction and grain boundaries, which always makes them the record-efficiency devices, are shown. More precisely, by employing a correlative microscopy approach, the typical fingerprints for superior properties of internal interfaces necessary for maintaining a lower recombination activity in the cell is discovered. These are a Cu-depleted and Cd-enriched CIGS absorber surface, near the p-n junction, as well as a negative Cu factor (∆β) and high Na content (>1.5 at%) at the grain boundaries. Thus, this work provides key factors governing the device performance (efficiency), which can be considered in the design of next-generation solar cells., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg 3 Sb 1.5 Bi 0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe-CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe-CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.

Solution synthesis of particles emerges as an alternative to prepare thermoelectric materials with less demanding processing conditions than conventional solid-state synthetic methods. However, solution synthesis generally involves the presence of additional molecules or ions belonging to the precursors or added to enable solubility and/or regulate nucleation and growth. These molecules or ions can end up in the particles as surface adsorbates and interfere in the material properties. This work demonstrates that ionic adsorbates, in particular Na + ions, are electrostatically adsorbed in SnSe particles synthesized in water and play a crucial role not only in directing the material nano/microstructure but also in determining the transport properties of the consolidated material. In dense pellets prepared by sintering SnSe particles, Na remains within the crystal lattice as dopant, in dislocations, precipitates, and forming grain boundary complexions. These results highlight the importance of considering all the possible unintentional impurities to establish proper structure-property relationships and control material properties in solution-processed thermoelectric materials., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Thermoelectric materials generate electric energy from waste heat, with conversion efficiency governed by the dimensionless figure of merit, ZT. Single-crystal tin selenide (SnSe) was discovered to exhibit a high ZT of roughly 2.2-2.6 at 913 K, but more practical and deployable polycrystal versions of the same compound suffer from much poorer overall ZT, thereby thwarting prospects for cost-effective lead-free thermoelectrics. The poor polycrystal bulk performance is attributed to traces of tin oxides covering the surface of SnSe powders, which increases thermal conductivity, reduces electrical conductivity and thereby reduces ZT. Here, we report that hole-doped SnSe polycrystalline samples with reagents carefully purified and tin oxides removed exhibit an ZT of roughly 3.1 at 783 K. Its lattice thermal conductivity is ultralow at roughly 0.07 W m -1  K -1 at 783 K, lower than the single crystals. The path to ultrahigh thermoelectric performance in polycrystalline samples is the proper removal of the deleterious thermally conductive oxides from the surface of SnSe grains. These results could open an era of high-performance practical thermoelectrics from this high-performance material., (© 2021. The Author(s).)

Powder metallurgy introduces small structures of high-density grain boundaries into Bi 2 Te 3 -based alloys, which promises to enhance their mechanical and thermoelectric performance. However, due to the strong donor-like effect induced by the increased surface, Te vacancies form in the powder-metallurgy process. Hence, the as-sintered n-type Bi 2 Te 3 -based alloys show a lower figure of merit (ZT) value than their p-type counterparts and the commercial zone-melted (ZM) ingots. Here, boron is added to one-step-sintered n-type Bi 2 Te 3 -based alloys to inhibit grain growth and to suppress the donor-like effect, simultaneously improving the mechanical and thermoelectric (TE) performance. Due to the alleviated donor-like effect and the carrier mobility maintained in our n-type Bi 2 Te 2.7 Se 0.3 alloys upon the addition of boron, the maximum and average ZT values within 298-473 K can be enhanced to 1.03 and 0.91, respectively, which are even slightly higher than that of n-type ZM ingots. Moreover, the addition of boron greatly improves the mechanical strength such as Vickers hardness and compressive strength due to the synergetic effects of Hall-Petch grain-boundary strengthening and boron dispersion strengthening. This facile and cost-effective grain boundary engineering by adding boron facilitates the practical application of Bi 2 Te 3 -based alloys and can also be popularized in other thermoelectric materials., (© 2021 Wiley-VCH GmbH.)