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- All Subjects: Materials Science
- Creators: Chizmeshya, Andrew
- Member of: Barrett, The Honors College Thesis/Creative Project Collection
Description
In materials science, developing GeSn alloys is major current research interest concerning the production of efficient Group-IV photonics. These alloys are particularly interesting because the development of next-generation semiconductors for ultrafast (terahertz) optoelectronic communication devices could be accomplished through integrating these novel alloys with industry-standard silicon technology. Unfortunately, incorporating a maximal amount of Sn into a Ge lattice has been difficult to achieve experimentally. At ambient conditions, pure Ge and Sn adopt cubic (α) and tetragonal (β) structures, respectively, however, to date the relative stability and structure of α and β phase GeSn alloys versus percent composition Sn has not been thoroughly studied. In this research project, computational tools were used to perform state-of-the-art predictive quantum simulations to study the structural, bonding and energetic trends in GeSn alloys in detail over a range of experimentally accessible compositions. Since recent X-Ray and vibrational studies have raised some controversy about the nanostructure of GeSn alloys, the investigation was conducted with ordered, random and clustered alloy models.
By means of optimized geometry analysis, pure Ge and Sn were found to adopt the alpha and beta structures, respectively, as observed experimentally. For all theoretical alloys, the corresponding αphase structure was found to have the lowest energy, for Sn percent compositions up to 90%. However at 50% Sn, the correspondingβ alloy energies are predicted to be only ~70 meV higher. The formation energy of α-phase alloys was found to be positive for all compositions, whereas only two beta formation energies were negative. Bond length distributions were analyzed and dependence on Sn incorporation was found, perhaps surprisingly, not to be directly correlated with cell volume. It is anticipated that the data collected in this project may help to elucidate observed complex vibrational properties in these systems.
By means of optimized geometry analysis, pure Ge and Sn were found to adopt the alpha and beta structures, respectively, as observed experimentally. For all theoretical alloys, the corresponding αphase structure was found to have the lowest energy, for Sn percent compositions up to 90%. However at 50% Sn, the correspondingβ alloy energies are predicted to be only ~70 meV higher. The formation energy of α-phase alloys was found to be positive for all compositions, whereas only two beta formation energies were negative. Bond length distributions were analyzed and dependence on Sn incorporation was found, perhaps surprisingly, not to be directly correlated with cell volume. It is anticipated that the data collected in this project may help to elucidate observed complex vibrational properties in these systems.
ContributorsLiberman-Martin, Zoe Elise (Author) / Chizmeshya, Andrew (Thesis director) / Sayres, Scott (Committee member) / Wolf, George (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
The story of graphene truly began in what was simply a stub in the journal Physical Review not two years after the end of World War II. In 1947, McGill University physicist P.R. Wallace authored “The Band Theory of Graphite” and attempted to develop a foundation on which the structure-property relationship of graphite could be explored; he calculates the number of free electrons and conductivity of what he describes as “a single hexagonal layer” and “suppos[es] that conduction takes place only in layers” in bulk graphite to predict wave functions, energies at specific atomic sites in the hexagonal lattice, and energy contours using a tight binding approximation for a hypothesized version of what we now call ‘armchair-style’ graphene. While Wallace was the first to explore the band structure and Brillouin Zones of single-layer graphite, the concept of two-dimensional materials was not new. In fact, for years, it was dismissed as a thermodynamic impossibility.
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.
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.
ContributorsShulman, Neal Arthur (Author) / Adams, James (Thesis director) / Islam, Rafiqul (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05