Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Mahale, Pratibha; Moradifar, Parivash; Cheng, Hiu Yan; Nova, Nabila Nabi; Grede, Alex J.; Lee, Byeongdu; De Jesús, Luis R.; Wetherington, Maxwell; Giebink, Noel C.; Badding, John V.; Alem, Nasim; Mallouk, Thomas E.

doi:10.1021/acsnano.0c03559

Title: Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Journal Article · Thu Sep 17 00:00:00 EDT 2020 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.0c03559· OSTI ID:1768849

Mahale, Pratibha ^[1]; Moradifar, Parivash ^[2]; Cheng, Hiu Yan ^[2]; Nova, Nabila Nabi ^[2]; Grede, Alex J. ^[2];

^[3]; De Jesús, Luis R. ^[1]; Wetherington, Maxwell ^[2];

^[2];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Pennsylvania State Univ., University Park, PA (United States)
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. In this work, we explore the synthesis and properties of a germanium metalattice in which the similar to 70 nm periodicity of a silica colloidal crystal template is close to the similar to 24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a coreshell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357; DMR-1420620

OSTI ID:: 1768849

Journal Information:: ACS Nano, Vol. 14, Issue 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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interconnected polycrystalline Ge
oxide free Ge
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Title: Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

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