Abstract
Oxide containing films were deposited by reactive sputtering using a high entropy alloy (HEA) target made of equal concentrations of the five 3d-transion metals: Cr, Fe, Co, Ni, and Cu. We report on controlled alterations to the electrical properties made by post-deposition heat treatments in oxidizing and reducing atmospheres respectively. The temperature coefficient of resistivity of the films could be varied between -1.2×10-3 K-1 through 0 and to +0.7×10-3 K-1, while the measured effective resistivity could be varied between 1.3×10-4 Ωcm and 1.2×10-3 Ωcm by post deposition processing. To study the transport mechanisms, we performed temperature dependent Hall effect measurements down to 10 K. We correlated the electrical behavior with structural measurements by a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) for elemental mapping at various length scales and secondary ions mass spectroscopy (SIMS). The key to engineering the resistivity is controlling the topology of the film. The topology of the as- deposited thin films can be controlled by the oxygen flow during reactive sputtering as the most important parameter. For zero oxygen flow we have obtained a homogenous HEA film having a FCC structure with the CrFeNiCoCu target. For high oxygen flow we have observed a high entropy oxide with a rock salt crystal structure. Here we report on the case of intermediate flow of oxygen. The as-deposited structure is then complex. There are nano sized regions with oxides and regions with FCC HEA alloys with different compositions of all the 3d-metals but also supersaturated with oxygen. The topology of these regions, and also their concentration, can be altered by post-deposition heat treatment. The transport in the HEA regions are dominated by alloy scattering. The potential in the FCC HEA has disorder due to the random mixing of the elements, which also gives distortion of the individual atom sites. This gives resistivities above the Mott- Ioffe-Regel limit while still having a positive TCR. These disorder effects will be further enhanced by the uptake of oxygen atoms. For these cases one gets weak localization, yielding a negative TCR. The oxides may be insulating but may also conduct by variable range hopping of the Efros–Shklovskii-type or the Mott- type yielding characteristic negative TCR. The post-deposition yields oxide segregation, of for example of spinel type containing Cr. This reduce the entropy and stability of the metal alloy, creating FCC and BCC metal alloys of different compositions. In the case of reducing the heat treatment in a reducing atmosphere, the oxides are reduced. The experimental resistivities are in excellent agreement with the model for the conduction.
