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Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.
To mitigate climate change, carbon needs to be removed from the atmosphere and stored for thousands of years. Currently, carbon removal and storage are voluntarily procured, and longevity of storage is inconsistently defined and regulated. Clauses can be added to procurement contracts to require long-term management and increase the durability of storage. Well-designed and properly enforced contracts can pave the way to future regulation for long-term carbon management.
With the rise of global warming and the growing energy crisis, scientists have pivoted from typical resources to look for new materials and technologies that can aid in advancing renewable energy efforts. Perovskite materials hold the potential for making high-efficiency, low-cost solar cells through solution processing of Earth abundant materials; however, scalability and manufacturability remain a challenge. In order to transition from small scale processing in inert environments via spin coating to higher throughput processing in ambient conditions via blade coating, the fundamentals of perovskite crystallization must be understood. Classical nucleation theory, the LaMer relation, and nonclassical crystallization considerations are discussed to provide a mechanism by which gellan gum, a nontoxic biopolymer from the food industry, has enabled quality halide perovskite thin films. Specifically, this research aims to study the effects of gellan gum in improving perovskite manufacturability by controlling crystallization through indirect alteration of evaporation and supersaturation rates by modifying fluid dynamics and the free energy associated with nucleation and growth. Simply, gellan gum controls crystallization to enable the fabrication of promising scalable PVSK devices in open air.