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Germanium nanoparticle nucleation was studied in organized arrays on HfO2 using a SiO2 thin film mask with ~20-24 nm pores and a 6×1010 cm-2 pore density. Poly(styrene-b-methyl methacrylate) diblock copolymer was employed to pattern the SiO2 film. Hot wire chemical vapor deposition produced Ge nanoparticles using 4-19 monolayer Ge exposures. By seeding adatoms on HfO2 at room temperature before growth and varying growth temperatures between 725-800 K, nanoparticle size was demonstrated to be limited by Ge etching of SiO2 pore walls.

A simple combinatorial approach for studying chemical and physical vapor deposition (CVD and PVD) nanoparticle growth is presented utilizing temperature and precursor flux gradients across sample surfaces. Large temperature gradients (450-700 °C) are induced covering the entire range of interest for most CVD and PVD processes. Precursor flux gradients may also be introduced simultaneously or separately using a tungsten cracking filament mounted on a translation arm. Theory and calibration experiments are explained and results from a study on Ge nanoparticle growth on HfO2 surfaces are presented and analyzed. This method drastically decreases experimental time required to investigate nanoparticle growth and identify optimum deposition conditions. Furthermore, this approach greatly facilitates preparation of library samples containing a wide range (several orders of magnitude) in variation of nanoparticle sizes, density, and composition for subsequent studies.

Ge is deposited on HfO2 surfaces by chemical vapor deposition (CVD) with GeH4. 0.7-1.0 ML GeHx (x = 0-3) is deposited by thermally cracking GeH4 on a hot tungsten filament. Ge oxidation and bonding are studied at 300-1000 K with X-ray photoelectron spectroscopy (XPS). Ge, GeH, GeO, and GeO2 desorption are measured with temperature programmed desorption (TPD) at 400-1000 K. Ge initially reacts with the dielectric forming an oxide layer followed by Ge deposition and formation of nanocrystals in CVD at 870 K. 0.7-1.0 ML GeHx deposited by cracking rapidly forms a contacting oxide layer on HfO2 that is stable from 300-800 K. Ge is fully removed from the HfO2 surface after annealing to 1000 K. These results help explain the stability of Ge nanocrystals in contact with HfO2.

This paper discusses a kinetically-driven patterning scheme to marry top-down and bottom-up assembly of nanoparticle arrays. We explain how Ge atoms interact with different dielectric surfaces to either etch the surface or to accumulate and self assemble into nanocrystals during chemical vapor deposition. By exploiting the different reactivity of these dielectrics, the accumulation of adatoms is controlled and thus subsequent self assembly of nanocrystals is controlled. Scanning electron microscopy and atomic force microscopy are used to determine particle densities. We have achieved dense (>1011 cm-2) arrays of self-assembled Ge nanocrystals within ∼100 µm sized features (defined by optical lithography) with no Ge deposition on the adjacent SiO2 sacrificial mask region. Electron beam lithography was used to pattern smaller (100 µm to 500 nm) features in which to direct the self assembly. As features shrink below 10 µm, nanoparticle nucleation within the feature is sharply affected. Finally, diblock copolymers are used to pattern 20 nm features to template self assembly of nanoparticles at a scale useful for device applications.

GeH4 is thermally cracked over a hot filament depositing 0.7–15 ML Ge onto 2–7 nm SiO2/Si(100) at substrate temperatures of 300–970 K. Ge, GeHx, GeO, and GeO2 desorption is monitored through temperature programmed desorption in the temperature range 300–1000 K. Ge bonding changes are analyzed during annealing from 300–1000 K with X-ray photoelectron spectroscopy (XPS). Low temperature desorption features are attributed to GeO and GeH4. No GeO2 desorption is observed, but GeO2 decomposition to Ge through high temperature pathways is seen above 700 K. Germanium oxidization results from Ge etching of the oxide substrate, which is demonstrated through XPS. Ge nanoparticle formation on SiO2 is demonstrated using the agglomeration process. With these results, explanations for the difficulties of conventional chemical vapor deposition to produce Ge nanocrystals on SiO2 surfaces are proposed.