Phase Separation In Solid State Research Articles

Volatile Solid Additive-Assisted Sequential Deposition Enables 18.42% Efficiency in Organic Solar Cells.

Morphology optimization of active layer plays a critical role in improving the performance of organic solar cells (OSCs). In this work, a volatile solid additive‐assisted sequential deposition (SD) strategy is reported to regulate the molecular order and phase separation in solid state. The OSC adopts polymer donor D18‐Cl and acceptor N3 as active layer, as well as 1,4‐diiodobenzene (DIB) as volatile additive. Compared to the D18‐Cl:N3 (one‐time deposition of mixture) and D18‐Cl/N3 (SD) platforms, the D18‐Cl/N3(DIB) device based on DIB‐assisted SD method exhibits a finer phase separation with greatly enhanced molecular crystallinity. The optimal morphology delivers superior charge transport and extraction, offering a champion power conversion efficiency of 18.42% with significantly enhanced short‐circuit current density (J sc) of 27.18 mA cm−2 and fill factor of 78.8%. This is one of the best performances in binary SD OSCs to date. Angle‐dependent grazing‐incidence wide‐angle X‐ray scattering technique effectively reveals the vertical phase separation and molecular crystallinity of the active layer. This work demonstrates the combination of volatile solid additive and sequential deposition is an effective method to develop high‐performance OSCs.

Microstructure tailoring of Al-containing compositionally complex alloys by controlling the sequence of precipitation and ordering

Refractory metal-based, Al-containing compositionally complex alloys (RCCA) are promising candidates for high-temperature structural applications. To shed light on the complex phase transitions, thermodynamic calculations were performed to select two representative alloys with different sequences in phase transitions. Samples of these compositions were synthesized by arc melting of pure elements followed by a homogenization treatment to experimentally verify the room temperature microstructure and assess the phase transitions. Differential scanning calorimetry (DSC), scanning (SEM) and transmission electron microscopy (TEM) studies after the homogenization and quenching revealed multiple distinct sequences of transitions: (i) 82(TaMoTi)-8Cr-10Al (in at.%) exhibits a solid-state phase separation concurrent with ordering of the precipitates. This results in a disordered matrix with ordered precipitates. Thermal analysis indicates that while cooling from the high-temperature A2 phase, the phase separation and ordering are spread out over a large temperature range (approx. 750 – 1250°C), with a peak at 1055°C. (ii) In the 77(TaMoTi)-8Cr-15Al alloy, a continuous phase transition at 1155°C leads to a single-phase B2 matrix with planar faults. At slightly lower temperatures (approx. 1096°C), phase separation occurs resulting in a B2 matrix with segregation at planar faults and A2 precipitates. In both investigated compositions, the A2 phase is enriched in Ta and Mo. Conversely, the B2 phase is enriched in Al and Ti, while Cr is uniformly distributed in the phases.

Controlling Molecule Aggregation and Electronic Spatial Coherence in the H-Aggregate and J-Aggregate Regime at Room Temperature.

Controlling molecule aggregation in polymer films is one of the key factors in understanding the links between properties and structures in organic semiconductors. Here, we used poly(3-hexylthiophene-2,5-diyl) (P3HT) as the model system. By doping the insulating polar additive poly (ethylene oxide) (PEO) into P3HT film and controlling the processing methods, we achieved the side-to-side H-aggregate and head-to-tail J-aggregate of P3HT molecules with different extents at room temperature. We have demonstrated that the solvent solidification rate plays an important role in the controlling of molecule aggregation, which finally influenced the solid-state phase separation in the film. Furthermore, based on a series of spectroscopy investigations, we quantified the electronic spatial coherence in different aggregations combined with the modified Franck–Condon model. Subsequently, we established the relationship between the processing method, the molecule aggregation, and the electronic spatial coherence.

Real-time observation of nanoscale topological transitions in epitaxial PbTe/CdTe heterostructures

The almost completely immiscible PbTe/CdTe heterostructure has recently become a prototype system for self-organized quantum dot formation based on solid-state phase separation. Here, we study by real-time transmission electron microscopy the topological transformations of two-dimensional PbTe-epilayers into, first, a quasi-one-dimensional percolation network and subsequently into zero-dimensional quantum dots. Finally, the dot size distribution coarsens by Ostwald ripening. The whole transformation sequence occurs during all stages in the fully coherent solid state by bulk diffusion. A model based on the numerical solution of the Cahn-Hilliard equation reproduces all relevant morphological and dynamic aspects of the experiments, demonstrating that this standard continuum approach applies to coherent solids down to nanometer dimensions. As the Cahn-Hilliard equation does not depend on atomistic details, the observed morphological transformations are general features of the model. To confirm the topological nature of the observed shape transitions, we developed a parameter-free geometric model. This, together with the Cahn-Hilliard approach, is in qualitative agreement with the experiments.

Multiscale Microstructures and Microstructural Effects on the Reliability of Microbumps in Three-Dimensional Integration.

The dimensions of microbumps in three-dimensional integration reach microscopic scales and thus necessitate a study of the multiscale microstructures in microbumps. Here, we present simulated mesoscale and atomic-scale microstructures of microbumps using phase field and phase field crystal models. Coupled microstructure, mechanical stress, and electromigration modeling was performed to highlight the microstructural effects on the reliability of microbumps. The results suggest that the size and geometry of microbumps can influence both the mesoscale and atomic-scale microstructural formation during solidification. An external stress imposed on the microbump can cause ordered phase growth along the boundaries of the microbump. Mesoscale microstructures formed in the microbumps from solidification, solid state phase separation, and coarsening processes suggest that the microstructures in smaller microbumps are more heterogeneous. Due to the differences in microstructures, the von Mises stress distributions in microbumps of different sizes and geometries vary. In addition, a combined effect resulting from the connectivity of the phase morphology and the amount of interface present in the mesoscale microstructure can influence the electromigration reliability of microbumps.

Solid-state phase separation in Zr–Y–Al–Co metallic glass

The present study shows that the as-melt-spun Zr28Y28Al22Co22 amorphous ribbon undergoes solid-state phase separation into Zr- and Y-rich regions when heated below the glass transition temperature (Tg). Dynamic mechanical measurements show that two types of low-temperature relaxation occur below Tg, and transmission electron microscopy observation confirms the solid-state phase-separated microstructure. The diffusion coefficient of solid-state phase separation is calculated by the measured separation distance.

Influence of lithium chloride on the morphology of flexible slabstock polyurethane foams and their plaque counterparts

In continuing efforts to understand urea phase connectivity in flexible polyurethane foams and its implications on physical properties, LiCl is used to alter the phase-separation behavior of slabstock foams. Comparisons are also drawn with plaque counterparts, which are prepared using the same polyol, isocyanate, and chain extender (water). LiCl is shown to alter the solid-state phase separation behavior of the foams and the plaques in a similar manner. This is confirmed using multiple characterization techniques, which provide information at different scale lengths. The foams and plaques with and without LiCl are shown to possess a microphase separated morphology with interdomain spacings of ca. 100 Å. SAXS and TEM reveal that addition of LiCl reduces the urea aggregation behavior, typical in slabstock polyurethane foams, leading to a loss in the urea phase macro connectivity. Hard segment ordering, as studied by WAXS and FTIR, is shown to be of a similar nature in the plaque and foam, which do not incorporate LiCl. Addition of LiCl leads to a loss in the segmental packing behavior, or micro level connectivity of the urea phase, in both the plaques and corresponding foams, as inferred from WAXS and FTIR. The LiCl additive interacts with the polyol soft segments in an insignificant manner as shown from FTIR and DMA. In addition, foams containing LiCl are found to possess more intact cell windows due to the influence of LiCl on reaction kinetics as well as its effect on the precipitation of the urea phase. The experimental observations are supported by quantum mechanical calculations using a density functional theory approach, where molecular interactions between LiCl and model ether, urethane, and urea compounds are investigated. Interaction geometries of most stable complexes and their stability energies are calculated. Stability energies of ether/LiCl, urethane/LiCl, and urea/LiCl were determined to be −189, −617, and −687 kJ/mol, respectively, reinforcing that LiCl interacts predominantly with urea hard segments and in a minimal manner with the polyol soft segments.

In-situ refractory intermetallic-based composites

With the ultimate objective of exploiting refractory intermetallics for high-temperature structural materials, several binary and ternary two-phase intermetallics/refractory-metal solid solutions were explored. The ductile solid solution is used to toughen the composite microstructure via in-situ phase separation. While the viability of ductile phase separation in solid state was briefly considered for systems such as Nb 3Al/Nb, much of the work focused on processing eutectic systems such as Cr 2Nb/Nb and (Nb,Mo) 5Si 3/Nb,Mo). This paper describes results obtained via containerless directional solidification of these high-melting eutectic alloys using an optical float-zone furnace. The observations are explained on the basis of solidification theory and parameters unique to the optical float-zone furnace. It is demonstrated that, by this technique, casting-defect- and macrosegregation-free material, with well-aligned microstructure, can be readily produced. Moreover, the potential to approach sub-micron laminate spacing at high growth rate in alloys with very high melting eutectics has also been established. Room-temperature bend test evaluation of directionally solidified material is discussed in light of prevailing theories of ductile phase toughening. The results of a preliminary exploration of the NbMoCrSiAl multicomponent system are presented, showing the prevalence of eutectic phase separation and the potential for improving oxidation resistance.