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Biological materials have been used in construction for as long as we have used wood and limestone; however, biotechnologies seem to offer the potential to grow materials to our specifications and even to allow complex structures to be self-assembled through biological processes. Several promising materials have been identified, including microbially induced calcium carbonate as a cement or mycelium grown on waste materials, which has potential as a structural or insulation material. These developments run parallel to a speculative design discourse – in which features future cities are grown, kept living and self-adapt – as well as research into engineered living materials (ELMs), at the cutting edge of material science and synthetic biology research into ELMs. This question invites a wide range of research contributions in which we identify, evaluate and speculate on the role that grown materials and structures will have on the future of construction. We invite not only experimental work on the latest method in this area but also critique and reflection beyond the ‘hype’ of these, potentially transformative, technologies and approaches.
The crystal structure of fulvestrant hydrate (ethyl acetate) has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional theory techniques. This solvate of fulvestrant crystallizes in space group R3 (#146) with a = 23.39188(16), c = 16.50885(13) Å, V = 7823.08(7) Å3, and Z = 9. The crystal structure is composed of triangular hydrogen-bonded chains of molecules around one of the threefold axes. The fluorinated ends of the molecules cluster around another threefold axis. Voids around a threefold axis occupy 8.1% of the unit cell volume, and are partially occupied by the water and ethyl acetate molecules. Both hydroxyl groups act as donors in O–H⋯O hydrogen bonds. These H-bonds form a large ring. The powder pattern has been submitted to ICDD® for inclusion in the Powder Diffraction File™ (PDF®).
The application of energy storage within transmission and distribution grids as non-wire alternative solutions (NWS) is hindered by the lack of readily available analysis tools, standardized planning processes, and practical know-how. This Element provides a theoretical basis along with examples and real-world case studies to guide grid planners in the siting, sizing, and lifetime techno-economic evaluation of storage systems. Many applications are illustrated including feeder peak shaving, feeder reliability improvements, transmission reliability, transmission congestion relief, and renewable integration. Three case studies, based on the author's consulting experience, illustrate the versatility of the analysis methods and provide a guide to grid planners while tackling real world problems.
Energy storage systems (ESS) exist in a wide variety of sizes, shapes and technologies. An energy storage system's technology, i.e. the fundamental energy storage mechanism, naturally affects its important characteristics including cost, safety, performance, reliability, and longevity. However, while the underlying technology is important, a successful energy storage project relies on a thorough and thoughtful implementation of the technology to meet the project's goals. A successful implementation depends on how well the energy storage system is architected and assembled. The system's architecture can determine its performance and reliability, in concert with or even despite the technology it employs. It is possible for an energy storage system with a good storage technology to perform poorly when implemented with a suboptimal architecture, while other energy storage systems with mediocre storage technologies can perform well when implemented with superior architectures.
In order to improve the resiliency of the grid and to enable integration of renewable energy sources into the grid, the utilization of battery systems to store energy for later demand is of the utmost importance. The implementation of grid-scale electrical energy storage systems can aid in peak shaving and load leveling, voltage and frequency regulation, as well as emergency power supply. Although the predominant battery chemistry currently used is Li-ion; due to cost, safety and sourcing concerns, incorporation of other battery technologies is of interest for expanding the breadth and depth of battery storage system installations. This Element discusses existing technologies beyond Li-ion battery storage chemistries that have seen grid-scale deployment, as well as several other promising battery technologies, and analyzes their chemistry mechanisms, battery construction and design, and corresponding advantages and disadvantages.
The structure, powder diffraction patterns and bandgap measurements of a series of manganese- and tungsten-containing alkaline-earth double perovskites (CaxSr2−x)MnWO6 (x = 0.25, 0.5, 0.75, 1.5, 1.75) have been investigated. Powder X-ray diffraction patterns of this series of compounds measured at room temperature have been submitted to be included in the Powder Diffraction File (PDF). These compounds crystallize in monoclinic space group P21/n (No.14). From (Ca1.75 Sr0.25)MnWO6 to (Ca0.25Sr1.75)MnWO6, lattice parameters a range from 5.6729(2) Å to 5.6774(4) Å, b from 5.5160(2) Å to 5.6638(4) Å, c from 7.8741(3) Å to 8.0051(4) Å, V from 240.39(2) Å3 to 257.410(12) Å3, and Z = 2. These compounds are pseudo-tetragonal. They all consist of distorted MnO6 and WO6 octahedra with rotational mismatch angles and tilt angles with respect to each other. For (CaxSr2−x)MnWO6, as x increases, the mismatch angles for MnO6 octahedra increase from 7.96 (6)° to 13.12(8)° and from 9.28(7)° to 14.87(9)° for WO6 octahedra. Correspondingly, the tilt angles range from 11.60(15)° to 14.20(3)° for MnO6, and from 13.34(2)° to 16.35(3)° for WO6. Bandgap measurements suggest that these compounds to be direct-allowed semiconductors with bandgaps ranging from 1.5 to 2.5 eV, indicating that members of (CaxSr2−x)MnWO6 are potential photocatalysts and photovoltaic materials that absorb visible light of the solar spectrum.
The crystal structure of merimepodib has been solved and refined using synchrotron X-ray powder diffraction data and optimized using density functional theory techniques. Merimepodib crystallizes in space group P212121 (#19) with a = 4.60827(3), b = 12.30400(14), c = 37.9583(4) Å, V = 2152.241(20) Å3, and Z = 4. The crystal structure is dominated by two chains of N–H⋯O hydrogen bonds along the a-axis. The solid-state conformation has a similar general shape to the minimum-energy conformation, but different orientations of several of the rings. The differences indicate that intermolecular interactions are important in determining the solid-state conformation. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).
The crystal structure of baricitinib has been solved and refined using synchrotron X-ray powder diffraction data and optimized using density functional techniques. Baricitinib crystallizes in space group I2/a (#15) with a = 11.81128(11), b = 7.06724(6), c = 42.5293(3) Å, β = 91.9280(4)°, V = 3548.05(5) Å3, and Z = 8. The crystal structure is characterized by hydrogen-bonded double layers parallel to the ab-planes. The dimers form a graph set R2,2(8). The sulfone ends of the molecules reside in the interlayer regions. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).
Corrosion is an important problem that engineers and scientists must overcome to avoid the collapse of structures, chemical processing plants, and metallic objects, which can lead to not only economic loss but also environmental and human losses. One of the simplest and most widely used methods to quantify corrosion rates (CRs) is the immersion test. The usual approach that has been used to date, to quantify the CR by this method, is to assume that the initial surface area of the corroding object remains constant over time. It is shown that such approximations underestimate the true CR and that they may lead to significant errors. A formula to calculate the CR considering changes in the area is presented in this work. The formula herein can be used to accurately quantify the CR by the immersion test and improve the quality of experimental data and the analysis and modeling of corrosion phenomena.
This chapter provides an overview of electromigration in metals, starting from the early studies on bulk metals to the current studies on copper interconnects. Asmicroelectronics technology advances, electromigration becomes an important reliability problem for on-chip interconnects, evolving from the microscale to the nanoscale in copper lines. Key concepts are introduced, including the electron wind force, the Blech short-length effects, and copper damascene interconnects.
In Chapter 8, the statistical nature of electromigration is described. Along with understanding of the basic physical degradation mechanisms, this is an important area of research due to the need for extrapolations from simple test structures to the product level. One has to keep in mind that electromigration testing is usually done on single-link structures. In some instances, a few links are stitched together in a series or parallel fashion, but massive-scale studies with large interconnect arrays have not been implemented yet as a standard testing methodology. Only the application of very large test structures with an extended amount of interconnect links encompassing metal lines and contacts/vias can lead to the detection of “early” or “extrinsic” failures, which are the limiting factor in the extrapolation to product-level interconnect systems. The detection of these early failures in electromigration and the complicated statistical nature of this important reliability phenomenon have been difficult issues to treat for decades in the past. In Chapter 8, an innovative technique utilizing large interconnect arrays in conjunction with the well-known Wheatstone Bridge are discussed, and both Al- and Cu-based interconnect technologies are described.
The momentum exchange between lattice atoms and conduction electrons together with the stress gradient along the metal wire embedded into the rigid confinement are two major driving forces for electromigration-induced evolution of stress and vacancy concentration. The growth of mechanical stress causes an evolution of a variety of defects that are inevitably present in the metal, leading to void formation. It affects the electrical properties of the interconnect. In order to estimate the time to failure caused by voiding, the kinetics of stress evolution should be resolved until the first void is nucleated. Then the analysis of the void size evolution should be performed in order to trace changes in resistances of individual voided lines and vias. In this chapter, we review the major results that have been achieved with the 1D phenomenological EM model. We demonstrate its capability to predict the transient and steady-state distributions of the vacancy concentration and the hydrostatic stress, a void nucleation, and its growth, and also a drift of small voids along a metal wire. Despite its simplified nature, the 1D model is capable of addressing the confinement effect of ILD/IMD dielectric on EM-induced degradation, and also the effect of metal grain structure.
A very different picture of the redistribution of metal density and stress, caused by electric stressing, can be expected in multibranch interconnect structures formed by connected metal lines within the same metal layer. The absence of diffusion barriers in line junctions allows atoms to freely migrate between lines along the trajectories of the current carriers. When a multibranch structure includes metal lines that are connected in parallel, the creation of a void in one of the parallel branches does not necessarily result in a failure, which contrasts with what happens in a single line segment, because current can continue to flow in the unvoided parallel lines. The on-chip power/ground (p/g) grid is an example of such electrically redundant multibranch structures. In this chapter, we review a recently developed assessment methodology of the p/g grid MTTF and describe a novel experimental technique that could validate the proposed methodology. EM assessment performed on the grids with tens of millions of nodes has shown that the formation of the first void alone didn’t cause a grid failure. A failure criterion of 10% voltage drop increase was met due to cumulative effect of nucleation of several voids and their growth in the failed branches.
In Chapter 5, we show that the microstructure and interfaces are important in controlling EM reliability of Cu damascene interconnects where the EM lifetime can be significantly improved with metal capping or alloying. In this chapter, we investigate the scaling effect on microstructure and the implication on EM reliability for Cu and Co damascene lines. The scaling effect on Cu microstructure was investigated using a high-resolution electron microdiffraction technique down to 22 nm linewidth for the 14 nm node. The results showed a systematic trend of microstructure evolution in Cu damascene lines with continued scaling. A Monte Carlo simulation was carried out to investigate grain growth in Cu interconnects beyond 22 nm linewidth based on total energy minimization. The simulation results enabled us to understand how the interface energy counteracts the strain and grain boundary energies to control the microstructure evolution in Cu lines with continued scaling. Then the scaling effect on microstructure evolution of Co damascene lines was investigated beyond the 10nm node using both electron microdiffraction and simulation. The simulated microstructures of Cu and Co interconnects are used to project the scaling effect on EM reliability beyond the 10 nm node.
An accurate analysis of the stress evolution in a metal line loaded with an electric current requires solution of a number of coupled partial differential equations (PDEs). The continuity equations, describing the evolution of concentrations of vacancies and plated atoms along the line, are linked with the force balance equation yielding the elastic stress evolution due to interaction of the metal line volumetric deformation with the rigid confinement. The electric current density distribution is found by solving the corresponding Laplace equation. Accounting for the polycrystalline structure of the metals used as conductors in on-chip interconnects, and proper consideration of a variety of venues for diffusion of vacancies, such as grain boundaries and interfaces with liners and capping layers, requires a comprehensive 2D or 3D analysis. Following void nucleation, which happens when the tensile stress reaches a critical value, the void shape and size are described by a combination of the Cahn–Hilliard and Allen–Kahn equations with the phase-field formalism. Detailed description of these coupled PDEs and results of their solution for a number of cases using finite element analysis (FEA) are demonstrated in this chapter. A good fit between simulation results and measurements is demonstrated throughout the chapter.
Scaling on-chip Cu wiring dimensions has degraded electromigration (EM) reliability with the same metallization and rapidly increased Cu resistivity. The size effects in EM and resistivity were caused by increased contributions from EM-induced mass flow and electron scattering with interfaces and grain boundaries, respectively. The EM Cu interconnect lifetime had further degraded by the decrease in the void volume required to cause EM failure. The Cu interconnect resistance was further increased by increasing the volume fraction of barrier/liner in metal wires that were required to produce chips with good reliability. In this chapter, we review the Cu microstructure and resistivity for various CMOS technological nodes, the basic physics of the EM phenomenon addressing EM mass transport, lifetime scaling rule, and damage formation in Cu damascene line structures. This is followed with discussions on Blech short length and EM scaling rule. Several techniques developed for improving EM reliability using upper-level dummy vias, impurities, Cu surface treatments, alternated liners, and surface metal coating are discussed together with the effects of Cu microstructure, atomic layer deposition MnOx liner, and Cu/carbon nanotube composite line on EM.Finally, the EM lifetimes, failure mechanisms and activation energies through various technological nodes are presented.