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There has been a surge in two-dimensional (2D) materials field since the discovery of graphene in 2004. Recently, a new class of layered atomically thin materials that exhibit in-plane structural anisotropy, such as black phosphorous, transition metal trichalcogenides and rhenium dichalcogenides (ReS2), have attracted great attention. The reduced symmetry in

There has been a surge in two-dimensional (2D) materials field since the discovery of graphene in 2004. Recently, a new class of layered atomically thin materials that exhibit in-plane structural anisotropy, such as black phosphorous, transition metal trichalcogenides and rhenium dichalcogenides (ReS2), have attracted great attention. The reduced symmetry in these novel 2D materials gives rise to highly anisotropic physical properties that enable unique applications in next-gen electronics and optoelectronics. For example, higher carrier mobility along one preferential crystal direction for anisotropic field effect transistors and anisotropic photon absorption for polarization-sensitive photodetectors.

This dissertation endeavors to address two key challenges towards practical application of anisotropic materials. One is the scalable production of high quality 2D anisotropic thin films, and the other is the controllability over anisotropy present in synthesized crystals. The investigation is focused primarily on rhenium disulfide because of its chemical similarity to conventional 2D transition metal dichalcogenides and yet anisotropic nature. Carefully designed vapor phase deposition has been demonstrated effective for batch synthesis of high quality ReS2 monolayer. Heteroepitaxial growth proves to be a feasible route for controlling anisotropic directions. Scanning/transmission electron microscopy and angle-resolved Raman spectroscopy have been extensively applied to reveal the structure-property relationship in synthesized 2D anisotropic layers and their heterostructures.
ContributorsChen, Bin, 1968- (Author) / Tongay, Sefaattin (Thesis advisor) / Bertoni, Mariana (Committee member) / Chang, Lan-Yun (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Layer structured two dimensional (2D) semiconductors have gained much interest due to their intriguing optical and electronic properties induced by the unique van der Waals bonding between layers. The extraordinary success for graphene and transition metal dichalcogenides (TMDCs) has triggered a constant search for novel 2D semiconductors beyond them. Gallium

Layer structured two dimensional (2D) semiconductors have gained much interest due to their intriguing optical and electronic properties induced by the unique van der Waals bonding between layers. The extraordinary success for graphene and transition metal dichalcogenides (TMDCs) has triggered a constant search for novel 2D semiconductors beyond them. Gallium chalcogenides, belonging to the group III-VI compounds, are a new class of 2D semiconductors that carry a variety of interesting properties including wide spectrum coverage of their bandgaps and thus are promising candidates for next generation electronic and optoelectronic devices. Pushing these materials toward applications requires more controllable synthesis methods and facile routes for engineering their properties on demand.

In this dissertation, vapor phase transport is used to synthesize layer structured gallium chalcogenide nanomaterials with highly controlled structure, morphology and properties, with particular emphasis on GaSe, GaTe and GaSeTe alloys. Multiple routes are used to manipulate the physical properties of these materials including strain engineering, defect engineering and phase engineering. First, 2D GaSe with controlled morphologies is synthesized on Si(111) substrates and the bandgap is significantly reduced from 2 eV to 1.7 eV due to lateral tensile strain. By applying vertical compressive strain using a diamond anvil cell, the band gap can be further reduced to 1.4 eV. Next, pseudo-1D GaTe nanomaterials with a monoclinic structure are synthesized on various substrates. The product exhibits highly anisotropic atomic structure and properties characterized by high-resolution transmission electron microscopy and angle resolved Raman and photoluminescence (PL) spectroscopy. Multiple sharp PL emissions below the bandgap are found due to defects localized at the edges and grain boundaries. Finally, layer structured GaSe1-xTex alloys across the full composition range are synthesized on GaAs(111) substrates. Results show that GaAs(111) substrate plays an essential role in stabilizing the metastable single-phase alloys within the miscibility gaps. A hexagonal to monoclinic phase crossover is observed as the Te content increases. The phase crossover features coexistence of both phases and isotropic to anisotropic structural transition.

Overall, this work provides insights into the controlled synthesis of gallium chalcogenides and opens up new opportunities towards optoelectronic applications that require tunable material properties.
ContributorsCai, Hui, Ph.D (Author) / Tongay, Sefaattin (Thesis advisor) / Dwyer, Christian (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2018