Autor: |
Thomas L. Sounart, Jun Liu, Mae Huo, Erik David Spoerke, Bonnie Beth McKenzie, James A. Voigt |
Rok vydání: |
2007 |
Předmět: |
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Zdroj: |
Journal of the American Chemical Society. 129(51) |
ISSN: |
1520-5126 |
Popis: |
Recently we discovered that under certain conditions new crystal growth (branch) can be induced on specific crystalline planes of the same material. This is a new phenomenon and is in sharp contrast to typical nucleation and growth in which a crystal will simply grow larger in preferred directions depending on the surface energy of the specific crystalline planes. Based on our observation, we developed a sequential nucleation and growth technique offering the power to assemble complex hierarchical crystals step-by-step. However, the key questions of when and how the secondary nucleation takes place have not been answered. Here we systematically study secondary ZnO crystal growth using organic diamine additives with a range of chain lengths and concentration. We found that ZnO branches form for a narrow diamine concentration range with a critical lower and upper critical nucleation concentration limit, which increases by about a factor of 5 for each additional carbon in the diaminoalkane chain. Our results suggest that the narrow window for secondary growth is dictated by the solubility of the ZnO crystals, where the low critical nucleation concentration is determined by slight etching of the surface to produce new nucleation sites, and the upper critical concentration is determined by the supersaturation concentration. Kinetic measurements show that the induction time and growth rate increase with increasing diamine concentration and follow classical nucleation and growth theory. Observations of branch morphological evolution reveal the mechanisms guiding the tunable crystal size and morphology. |
Databáze: |
OpenAIRE |
Externí odkaz: |
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