Surface chemistry of FeHx with dielectric surfaces : towards directed nanocrystal growth

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Winkenwerder, Wyatt August, 1981-

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The surface chemistry of GeH[subscript x] with dielectric surfaces is relevant to the application of germanium (Ge) nanocrystals for nanocrystal flash memory devices. GeH[subscript x] surface chemistry was first explored for thermally-grown SiO₂ revealing that GeH[subscript x] undergoes two temperature dependent reactions that remove Ge from the SiO₂ surface as GeH₄ and Ge, respectively. Ge only accumulates due to reactions between GeH[subscript x] species that form stable Ge clusters on the SiO₂ surface. Next, a Si-etched SiO₂ surface is probed by GeH[subscript x] revealing that the Si-etching defect activates the surface toward Ge deposition. The activation involves two separate reactions involving, first, the capture of GeH[subscript x] by the defect and second, a reaction between the captured Ge and remaining GeH[subscript x] species leading to the formation of Ge clusters. Reacting the defect with diborane, deactivates it toward GeH[subscript x] and also deactivates intrinsic hydroxyl groups toward GeH[subscript x] adsorption. A structure is proposed for the Si-etching defect. The surface chemistry of GeHx with HfO₂ is studied showing that the hafnium germinate that forms beneath the Ge nanocrystals exists as islands and not a continuous film. Annealing the hafnium germinate under a silane atmosphere will reduce it to Ge while leading to the deposition of hafnium silicate (HfSiO[subscript x]) and silicon (Si). Treating the HfO₂ with silane prior to Ge nanocrystal growth yields a surface with hafnium silicate islands on which Si also deposits. Ge deposition on this surface leads to the suppression of hafnium germinate formation. Electrical testing of capacitors made from Ge nanocrystals and HfO₂ shows that Ge nanocrystals encapsulated in Si/HfSiO[subscript x] layers have greatly improved retention characteristics.