Crystal Splitting in the Growth of Bi2S3 Page: 4 of 23
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O'Brien et al recently reported using bismuth acetate with corresponding elemental chalcogen
in refluxing octylamine to make bismuth chalcogenides nanostructures [12], and later on
extended the method to antimony chalcogenides nanostructures [18]. Nanorods of Bi2S3 and
hexagonal wafers of Bi2Se3 and Bi2Te3 were obtained, indicating a correlation between the
crystalline structure and resulting morphology of the nanomaterials. Fang et al [19] also reported
synthesis of Bi2Te3 hexagonal nanoplatelets with high uniformity in size and shape by a reaction
between bismuth 2-hexylhexanoate and trioctylphosphine telluride in the presence of oleic acid at
150 C.
In our synthesis, with the reaction between bismuth acetate complexed with oleic acid and
elemental sulfur in a noncoordinating solvent 1-octadecence, we obtained novel Bi2S3
nanostructures. Figure lA shows a representative transmission electron microscope (TEM) image
of such Bi2S3 nanostructures. They look like a wheat sheaf, as if a bundle of filamentary
crystals have been bandaged in its middle with the top and bottom fanning out while the middle
remaining thin -hence the name "sheaf structures". The individual nanofilaments have an
average diameter of 9 nm and the sheaves are - 570 nm in length.
Although the double-sheaf morphology dominates in our synthesis product, complex
structures made of 3-6 half-sheaves originating from the same core as well as half-sheaf
structures with a V-shape were also obtained. For example, Figure 1B shows a half-sheaf
structure, while Figure 1C and D shows rather symmetric structures formed by the intergrowth of
two or three double-sheaves from the same core. High resolution TEM analysis on the core part
of the multiple-sheaf structures may be expected to provide structural information which may
help understand why such structures form, however, the thickness of the core part and the strong
electron scattering from bismuth has made such measurements unattainable. Recently several
research groups [20-22] reported the formation of MnO multipods (each pod is a nanorod
terminated with diamond-like arrows). These MnO multipods relate to the Bi2S3 structures shown
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Tang, Jing & Alivisatos, A. Paul. Crystal Splitting in the Growth of Bi2S3, article, June 15, 2006; Berkeley, California. (https://digital.library.unt.edu/ark:/67531/metadc885164/m1/4/: accessed April 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.