Showing papers on "Grain boundary published in 2016"

Self-formed grain boundary healing layer for highly efficient CH 3 NH 3 PbI 3 perovskite solar cells

Abstract: Perovskite solar cells have attracted significant research efforts due to their remarkable performance, with certified power conversion efficiency now reaching 22%. Solution-processed perovskite thin films are polycrystalline, and grain boundaries are thought to be responsible for causing recombination and trapping of charge carriers. Here we report an effective and reproducible way of treating grain boundaries in CH3NH3PbI3 films deposited by means of a Lewis acid–base adduct approach. We show by high-resolution transmission electron microscopy lattice images that adding 6 mol% excess CH3NH3I to the precursor solution resulted in a CH3NH3I layer forming at the grain boundaries. This layer is responsible for suppressing non-radiative recombination and improving hole and electron extraction at the grain boundaries by forming highly ionic-conducting pathways. We report an average power conversion efficiency of 20.1% over 50 cells (best cell at 20.4%) together with significantly reduced current–voltage hysteresis achieved by this grain boundary healing process. The grain boundaries in thin-film perovskite solar cells are responsible for non-radiative carrier recombination, which is deleterious for the optoelectronic performance. Son et al. show how to passivate the grain boundaries by using excess CH3NH3I in the precursor solution, achieving efficiencies of 20.4%.

Grain boundary dominated ion migration in polycrystalline organic–inorganic halide perovskite films

Abstract: The efficiency of perovskite solar cells is approaching that of single-crystalline silicon solar cells despite the presence of a large grain boundary (GB) area in the polycrystalline thin films. Here, by using a combination of nanoscopic and macroscopic level measurements, we show that ion migration in polycrystalline perovskites dominates through GBs. Atomic force microscopy measurements reveal much stronger hysteresis both for photocurrent and dark-current at the GBs than on the grain interiors, which can be explained by faster ion migration at the GBs. The dramatically enhanced ion migration results in the redistribution of ions along the GBs after electric poling, in contrast to the intact grain area. The perovskite single-crystal devices without GBs show negligible current hysteresis and no ion-migration signal. The discovery of dominating ion migration through GBs in perovskites can lead to broad applications in many types of devices including photovoltaics, memristors, and ion batteries.

Stabilizing nanostructures in metals using grain and twin boundary architectures

Abstract: Forming alloys with impurity elements is a routine method for modifying the properties of metals. An alternative approach involves the incorporation of interfaces into the crystalline lattice to enhance the metal's properties without changing its chemical composition. The introduction of high-density interfaces in nanostructured materials results in greatly improved strength and hardness; however, interfaces at the nanoscale show low stability. In this Review, I discuss recent developments in the stabilization of nanostructured metals by modifying the architectures of their interfaces. The amount, structure and distribution of several types of interfaces, such as high- and low-angle grain boundaries and twin boundaries, are discussed. I survey several examples of materials with nanotwinned and nanolaminated structures, as well as with gradient nanostructures, describing the techniques used to produce such samples and tracing their exceptional performances back to the nanoscale architectures of their interfaces. The incorporation of structural defects, in particular of interfaces, into crystalline lattices results in enhanced material properties. In this Review, different types of boundaries and interfaces are discussed, including high- and low-angle grain boundaries, twin boundaries, nanotwinned and nanolaminated structures, and gradient nanostructures.

Li7La3Zr2O12 Interface Modification for Li Dendrite Prevention

Abstract: Al-contaminated Ta-substituted Li7La3Zr2O12 (LLZ:Ta), synthesized via solid-state reaction, and Al-free Ta-substituted Li7La3Zr2O12, fabricated by hot-press sintering (HP-LLZ:Ta), have relative densities of 92.7% and 99.0%, respectively. Impedance spectra show the total conductivity of LLZ:Ta to be 0.71 mS cm–1 at 30 °C and that of HP-LLZ:Ta to be 1.18 mS cm–1. The lower total conductivity for LLZ:Ta than HP-LLZ:Ta was attributed to the higher grain boundary resistance and lower relative density of LLZ:Ta, as confirmed by their microstructures. Constant direct current measurements of HP-LLZ:Ta with a current density of 0.5 mA cm–2 suggest that the short circuit formation was neither due to the low relative density of the samples nor the reduction of Li–Al glassy phase at grain boundaries. TEM, EELS, and MAS NMR were used to prove that the short circuit was from Li dendrite formation inside HP-LLZ:Ta, which took place along the grain boundaries. The Li dendrite formation was found to be mostly due to the i...

Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells.

Abstract: Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

The microstructure, mechanical properties and corrosion resistance of 316 L stainless steel fabricated using laser engineered net shaping

Abstract: The mechanical properties and corrosion resistance of 316 L stainless steel fabricated using the Laser Engineered Net Shaping (LENS) technique have been studied. The crack-free, full density samples made using SS316L alloy powder and the LENS technique are characterized by an unusual distinct dual-phase microstructure. STEM analysis revealed a significant increase of Cr and Mo content and a decrease of Ni in the grain boundaries. Based on the Cr and Ni content (austenite stabilizing elements), the Schaeffler diagram and the EBSD results, the existence of intercellular delta ferrite on subgrain boundaries and austenite in the fine-grains are observed. The XRD patterns, in addition to the FCC austenite phase, revealed the second BCC ferrite phase. Moreover, the sigma (FeCr) phases are present in the analyzed 316 L stainless steel. The occurrence of ferrite, which does not occur in regular stainless steel fabricated using conventional metallurgical methods, improves the mechanical and corrosion properties of the LENS-fabricated sample made using 316 L stainless steel powder. The obtained results prove that the microstructure of the SS316L fabricated using LENS is heterogeneous; its impact on the mechanical properties is visible. The analyzed samples are characterized by anisotropic mechanical properties that are favorable. For both the perpendicular and parallel directions of tensile tests, samples had a ductile fracture with many dimples inside of the larger dimples. The corrosion potential of SS316L LENS and classically manufactured steel is similar. The SS316L fabricated using LENS is characterized by a relatively low value of corrosion current density, which translates into much smaller corrosion rates.

Is Excess PbI2 Beneficial for Perovskite Solar Cell Performance

Abstract: Unreacted lead iodide is commonly believed to be beneficial to the efficiency of methylammonium lead iodide perovskite based solar cells, since it has been proposed to passivate the defects in perovskite grain boundaries. However, it is shown here that the presence of unreacted PbI2 results in an intrinsic instability of the film under illumination, leading to the film degradation under inert atmosphere and faster degradation upon exposure to illumination and humidity. The perovskite films without lead iodide have improved stability, but lower efficiency due to inferior film morphology (smaller grain size, the presence of pinholes). Optimization of the deposition process resulted in PbI2-free perovskite films giving comparable efficiency to those with excess PbI2 (14.2 ± 1.3% compared to 15.1 ± 0.9%) Thus, optimization of the deposition process for PbI2-free films leads to dense, pinhole-free, large grain size perovskite films which result in cells with high efficiency without detrimental effects on the film photostability caused by excess PbI2. However, it should be noted that for encapsulated devices illuminated through the substrate (fluorine-doped tin oxide glass, TiO2 film), film photostability is not a key factor in the device degradation.

Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p-Type Polycrystalline SnSe.

Abstract: Recent findings about ultrahigh thermoelectric performance in SnSe single crystals have stimulated related research on this simple binary compound, which is focused mostly on its polycrystalline counterparts, and particularly on electrical property enhancement by effective doping. This work systematically investigated the thermoelectric properties of polycrystalline SnSe doped with three alkali metals (Li, Na, and K). It is found that Na has the best doping efficiency, leading to an increase in hole concentration from 3.2 × 10(17) to 4.4 × 10(19) cm(-3) at room temperature, accompanied by a drop in Seebeck coefficient from 480 to 142 μV/K. An equivalent single parabolic band model was found adequate to capture the variation tendency of Seebeck coefficient with doping levels within a wide range. A mixed scattering of carriers by acoustic phonons and grain boundaries is suitable for numerically understanding the temperature-dependence of carrier mobility. A maximum ZT of ∼0.8 was achieved in 1% Na- or K-doped SnSe at 800 K. Possible strategies to improve the mobility and ZT of polycrystals were also proposed.

Electron beam melted Ti–6Al–4V: Microstructure, texture and mechanical behavior of the as-built and heat-treated material

Abstract: Electron Beam Melting (EBM), a powder bed additive layer manufacturing process, was used to produce Ti–6Al–4V specimens, whose microstructure, texture, and tensile properties were fully characterized. The microstructure, analyzed by optical microscopy, SEM/EBSD and X-ray diffraction, consists in fine α lamellae. Numerical reconstruction of the parent β phase highlighted the columnar morphology of the prior β grains, growing along the build direction upon solidification of the melt pool. The presence of grain boundary αGB along the boundaries of these prior β grains is indicative of the diffusive nature of the β→α phase transformation. Texture analysis of the reconstructed high temperature β phase revealed a strong pole in the build direction. For mechanical characterization, tensile specimens were produced using two different build themes and along several build orientations, revealing that vertically built specimens exhibit a lower yield strength than those built horizontally. The effect of post processing, either mechanical or thermal, was extensively investigated. The influence of surface finish on tensile properties was clearly highlighted. Indeed, mechanical polishing induced an increase in ductility – due to the removal of critical surface defects – as well as a significant increase of the apparent yield strength – caused by the removal of a ~150 µm rough surface layer that can be considered as mechanically inefficient and not supporting any tensile load. Thermal post-treatments were performed on electron beam melted specimens, revealing that subtransus treatments induce very moderate microstructural changes, whereas supertransus treatments generate a considerably different type of microstructure, due to the fast β grain growth occurring above the transus. The heat treatments investigated in this work had a relatively moderate impact on the mechanical properties of the parts.

Biexciton Emission from Edges and Grain Boundaries of Triangular WS2 Monolayers

Abstract: Monolayer tungsten disulfides (WS2) constitute a high quantum yield two-dimensional (2D) system, and can be synthesized on a large area using chemical vapor deposition (CVD), suggesting promising nanophotonics applications. However, spatially nonuniform photoluminescence (PL) intensities and peak wavelengths observed in single WS2 grains have puzzled researchers, with the origins of variation in relative contributions of excitons, trions, and biexcitons to the PL emission not well understood. Here, we present nanoscale PL and Raman spectroscopy images of triangular CVD-grown WS2 monolayers of different sizes, with these images obtained under different temperatures and values of excitation power. Intense PL emissions were observed around the edges of individual WS2 grains and the grain boundaries between partly merged WS2 grains. The predominant origin of the main PL emission from these regions changed from neutral excitons to trions and biexcitons with increasing laser excitation power, with biexcitons completely dominating the PL emission for the high-power condition. The intense PL emission and the preferential formation of biexcitons in the edges and grain boundaries of monolayer WS2 were attributed to larger population of charge carriers caused by the excessive incorporation of growth promoters during the CVD, suggesting positive roles of excessive carriers in the PL efficiency of TMD monolayers. Our comprehensive nanoscale spectroscopic investigation sheds light on the dynamic competition between exciton complexes occurring in monolayer WS2, suggesting a rich variety of ways to engineer new nanophotonic functions using 2D transition metal dichalcogenide monolayers.

Extreme creep resistance in a microstructurally stable nanocrystalline alloy

Abstract: A nanocrystalline copper–tantalum alloy with high strength and extremely high-temperature creep resistance is achieved via a processing method that creates clusters of atoms within the alloy that pin grain boundaries. Reducing the grain size of a metal is one way of increasing its strength, but it can often have detrimental effects on other mechanical properties. The resistance to slow irreversible deformation known as creep, for example, can be greatly diminished, owing to the relatively large volume of the material that is in the form of grain boundaries between the nanocrystalline constituents. Kristopher Darling et al. describe a family of nanostructured alloys that combine high strength with extremely high creep resistance. Key to this achievement is a processing strategy that creates tiny clusters at the grain boundaries, stabilizing the nanocrystalline grains against sliding, rotation and diffusional growth, and so greatly enhancing their resistance to creep. Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size1. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper2,3. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation3. Here we show that nanocrystalline copper–tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength4,5, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10−6 per second—six to eight orders of magnitude lower than most nanocrystalline metals—at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of microstructurally stable structural alloys with high strength and creep resistance for various high-temperature applications, including in the aerospace, naval, civilian infrastructure and energy sectors.

Understanding of the Extremely Low Thermal Conductivity in High-Performance Polycrystalline SnSe through Potassium Doping

Abstract: P-type polycrystalline SnSe and K0.01Sn0.99Se are prepared by combining mechanical alloying (MA) and spark plasma sintering (SPS). The highest ZT of ≈0.65 is obtained at 773 K for undoped SnSe by optimizing the MA time. To enhance the electrical transport properties of SnSe, K is selected as an effective dopant. It is found that the maximal power factor can be enhanced significantly from ≈280 μW m−1 K−2 for undoped SnSe to ≈350 μW m−1 K−2 for K-doped SnSe. It is also observed that the thermal conductivity of polycrystalline SnSe can be enhanced if the SnSe powders are slightly oxidized. Surprisingly, after K doping, the absence of Sn oxides at grain boundaries and the presence of coherent nanoprecipitates in the SnSe matrix contribute to an impressively low lattice thermal conductivity of ≈0.20 W m−1 K−1 at 773 K along the sample section perpendicular to pressing direction of SPS. This extremely low lattice thermal conductivity coupled with the enhanced power factor results in a record high ZT of ≈1.1 at 773 K along this direction in polycrystalline SnSe.

Influence of post heat treatments on anisotropy of mechanical behaviour and microstructure of Hastelloy-X parts produced by selective laser melting

Abstract: Selective laser melting (SLM) was used to fabricate tensile specimens using Hastelloy-X pre-alloyed powder. Mechanical behaviour at room temperature, normal and parallel to building direction, was investigated. Furthermore, as-fabricated tensile samples were compared with ones post processed by heat treatments (HT), hot isostatic pressing (HIP) and a combination of both (HIP+HT). Yield strength (YS), ultimate tensile strength (UTS) and elongation to failure (e f ) were analysed and explained based on the microstructure evolution. Dendrites and molten pool boundaries are mainly responsible for the observed anisotropy in e f of horizontal and vertical samples in the as-fabricated condition. After their dissolution by HT an increase in e f was observed. The columnar grain structure also contributes to the observed anisotropy in e f , inducing more ductile and cleavage like fracture surfaces in vertical and horizontal samples, respectively. The removal of porosity after HIP and HIP+HT yields a positive effect on e f . HIP or HT after SLM reduces the YS due to recovery processes such as dislocation density reduction and rearrangement of these dislocations in subgrain boundaries. Carbides of the type M x C y were partially segregated at the grain boundaries after HIP with detrimental effect on e f .

Surface and Interface Aspects of Organometal Halide Perovskite Materials and Solar Cells.

Abstract: The current challenges (eg, stability, hysteresis, etc) in organometal halide perovskite solar cell research are closely correlated with surfaces and interfaces For instance, efficient generation of charges, extraction, and transport with minimum recombination through interlayer interfaces is crucial to attain high-efficiency solar cell devices Furthermore, intralayer interfaces may be present in the form of grain boundaries within a film composed of the same material, for example, a polycrystalline perovskite layer The adjacent grains may assume different crystal orientations and/or have different chemical compositions, which impacts charge excitation and dynamics and thereby the overall solar cell performance In this Perspective, we present case studies to demonstrate (1) how surfaces and interfaces can impact material properties and device performance and (2) how these issues can be investigated by surface science techniques, such as scanning probe microscopy, photoelectron spectroscopy, and so

Misorientation-angle-dependent electrical transport across molybdenum disulfide grain boundaries

Abstract: Grain boundaries in monolayer transition metal dichalcogenides have unique atomic defect structures and band dispersion relations that depend on the inter-domain misorientation angle. Here, we explore misorientation angle-dependent electrical transport at grain boundaries in monolayer MoS2 by correlating the atomic defect structures of measured devices analysed with transmission electron microscopy and first-principles calculations. Transmission electron microscopy indicates that grain boundaries are primarily composed of 5-7 dislocation cores with periodicity and additional complex defects formed at high angles, obeying the classical low-angle theory for angles <22°. The inter-domain mobility is minimized for angles <9° and increases nonlinearly by two orders of magnitude before saturating at ∼ 16 cm(2) V(-1) s(-1) around misorientation angle ≈ 20°. This trend is explained via grain-boundary electrostatic barriers estimated from density functional calculations and experimental tunnelling barrier heights, which are ≈ 0.5 eV at low angles and ≈ 0.15 eV at high angles (≥ 20°).

Grain-Size-Limited Mobility in Methylammonium Lead Iodide Perovskite Thin Films

Abstract: We report a systematic study of the gigahertz-frequency charge carrier mobility found in methylammonium lead iodide perovskite films as a function of average grain size using time-resolved microwave conductivity and a single processing chemistry. Our measurements are in good agreement with the Kubo formula for the AC mobility of charges confined within finite grains, suggesting (1) that the surface grains imaged via scanning electron microscopy are representative of the true electronic domain size and not substantially subdivided by twinning or other defects not visible by microscopy and (2) that the time scale of diffusive transport across grain boundaries is much slower than the period of the microwave field in this measurement (∼100 ps). The intrinsic (infinite grain size) minimum mobility extracted form the model is 29 ± 6 cm2 V–1 s–1 at the probe frequency (8.9 GHz).

Ferroelectricity in undoped-HfO2 thin films induced by deposition temperature control during atomic layer deposition

Abstract: HfO2 thin films, extensively studied as high-k gate dielectric layers in metal-oxide-semiconductor field effect transistors, have attracted interest of late due to their newly discovered ferroelectricity in doped HfO2. The appearance of the ferroelectric orthorhombic phase of HfO2 was previously examined in variously doped and undoped systems, but the effects of process-variable changes on the physical and chemical characteristics of a thin film and the resulting ferroelectricity have not been studied systematically. Here, the evolution of ferroelectricity in HfO2 thin films through deposition temperature control during atomic layer deposition was systematically examined without the intentional doping of metallic elements other than Hf. The lower-temperature-deposited HfO2 showed an increased impurity concentration, which was mainly carbon, and the involvement of these impurities suppressed the lateral grain growth during the crystallization thermal treatment. The grain size reduction could stabilize the metastable orthorhombic phase, whose surface and grain boundary energies are lower than those of the room-temperature-stable monoclinic phase, by increasing the grain boundary areas. The 9 nm-thick HfO2 thin film deposited at 220 °C exhibited a remanent polarization value of 10.4 μC cm−2 and endured up to 108 switching cycles, which is a 102-fold improvement compared to the previously reported undoped 6 nm-thick HfO2. This can be ascribed to the decrease in the relative portion of defective interfacial layers by increasing the total film thickness. The strategy of using deposition temperature control is a feasible method for the fabrication of these new lead-free binary ferroelectric thin films.