Abstract

ZnO thin films and nanostructures are applied in various devices due to their interesting optical and electrical properties. Atomic layer deposition (ALD) of ZnO offers unique advantages such as precise thickness control, uniformity, and conformality. Using reactive plasma species as the co‐reactant (PE‐ALD) allows further enhancement of the material characteristics and tunable properties. The substrate temperature has been reported to be the most influential parameter in this technique, as it affects the growth per cycle (GPC) and material properties. However, an investigation on how the film properties are linked to the GPC is lacking in the literature. Herein, the temperature dependence of several material properties is found closely related to the GPC. The preferential crystal orientation switches from (100) to (002) up to the constant region of the GPC versus temperature, the so‐called ALD window. Refractive index and mass density show different slopes in temperature regions outside and within the ALD window. Excitonic absorption is only found for films prepared within the ALD window, and the resistivity drops rapidly above the ALD window. Following these results, more insights can be gained on the ALD growth (especially the role of the ALD window) and ideal temperature ranges for specific applications.

Highlights

  • ZnO thin films and nanostructures are applied in various devices due to their interesting optical and electrical properties

  • In the range of 125 to 200 C, the growth per cycle (GPC) was constant and we identified this region as the so-called Atomic layer deposition (ALD) window.[10]

  • The thickness deposited per cycle in the ALD window with a value around 2.5 Å is comparable with the interplanar spacing along the c-axis of the ZnO wurtzite crystal structure (2.60 Å)

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Summary

Results and Discussion

For temperatures above the ALD window, the GPC increases to values larger than the (002) interplanar spacing, whereas the XRD results show a strong preferential (002) orientation In this temperature region, the growth cannot happen in a monolayer-by-monolayer fashion anymore but includes a CVD-component in the mechanism. A red shift of the absorption edge has been observed in annealing procedures of ZnO, associated with an enhanced removal of intrinsic defects and improved crystallinity at a higher annealing temperature.[51,52] The absorption edge increases by around 30 meV when the substrate temperature is further increased from 225 to 250 C Films prepared (slightly) above the ALD window showed lower resistivity and high transmission, pointing out a possible application (with Al doping) for transparent conductive oxides.[2]

Conclusion
Experimental Section
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