We demonstrate memory property using Ni nanocrystals with mean diameter of 9nm embedded in HfO2 high-k dielectric that are formed via a self-assembly process by sputtering and rapid thermal annealing. X-ray photoelectron spectroscopy shows that Ni penetrates into the 5nm HfO2 after high temperature annealing above 800°C in N2. However, the diffusion is suppressed by N incorporation into HfO2 by NH3 annealing. Metal-oxide-semiconductor structures were fabricated with Ni nanocrystals embedded in HfO2. An additional counterclockwise hysteresis of 2.1V due to the charge trapping properties of the Ni nanocrystals was observed from a ±5V sweep during capacitance–voltage electrical measurement.

Formation of Ge nanocrystals embedded in HfAlO high-k dielectric by co-sputtering of HfO2, Al2O3, and Ge, followed by rapid thermal annealing was demonstrated. Analysis by transmission electron microscopy and x-ray photoelectron spectroscopy confirmed the formation of nonoxidized Ge nanocrystals with a minimum size of about 5nm embedded in HfAlO dielectric. We also demonstrated the application of such nanocrystals in nonvolatile memory devices, achieving a 2.2V memory window as obtained from the C–V characterization of the memory device.

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The in situ deposition process of SiGe nanocrystals on SiO2 and HfO2 substrates was studied using Auger electron spectroscopy, atomic force microscopy, and x-ray photoelectron spectroscopy. The Ge concentration in SiGe nanocrystals increased with deposition time at equal Si/Ge flow rates. Analysis indicated that the nucleation of Ge takes place preferentially on prenucleated Si on the dielectric. Memory transistors were fabricated using SiGe nanocrystals and HfO2 tunneling/control dielectrics as a gate stack. Memory effects from floating SiGe nanocrystals in HfO2 were clearly observed at room temperature from metal–oxide–semiconductor field effect transistor devices with a threshold voltage shift of about 0.5 V with the application of +4 V.

The etching properties of HfO based high dielectric constant (K) films, HfO2, HfON, HfSiO, and HfAlO, were investigated using inductively coupled plasma of Cl2/HBr/CHF3/CF4/O2. The etch rates varied depending on the chemical components in the films. Among HfO2, HfON, HfSiO, and HfAlO, the etch rates of HfSiO increased most significantly with increasing radio frequency bias power. This may be attributed to the ternary network of Hf–Si–O that is different from the binary network of other films of Hf–O, Hf–N, Si–O, and Al–O. The etch rates of HfON were higher than those of HfO2 due to the effect of the high Hf–N etch rates compared to the Hf–O etch rates, whereas the HfAlO etch rates were lower than those of HfO2 due to the effect of the low Al–O etch rates. Etch residues and chemical compositions of HfO based dielectrics were analyzed by x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. A significant amount of fluorides existed on the surface after CF4/CHF3 etching whereas only a small amount of chloride and bromide existed after Cl2/HBr etching. The high temperature post-treatment step was effective in reducing the amount of residues.