Cobalt oxide (CoOx) thin films were deposited on thermally grown SiO2 substrates by atomic layer deposition (ALD) using bis(1,4-di-iso-propyl-1,4-diazabutadiene)cobalt (C16H32N4Co) and oxygen (O2) as reactants at deposition temperatures ranging from 125 to 300 °C. X-ray diffraction (XRD) and Raman spectroscopic analysis indicated that a mixed-phase oxide consisting of CoO and Co3O4 was deposited at temperatures ranging from 125 to 250 °C. However, single-phase Co3O4 was deposited above the deposition temperature of 275 °C. Further, analyses by Rutherford backscattering spectrometry, transmission electron microscopy, and selected area electron diffraction along with XRD and Raman spectroscopy revealed that the single-phase cobalt oxide film was stoichiometric crystalline (spinel structure) with negligible N and C impurities. The optical band gap of the single-phase Co3O4 film was 1.98 eV and increased with decreasing deposition temperature. It was also shown that the mixed-phase cobalt oxide thin films could be converted into single-phase spinel Co3O4 by annealing at 350 °C in O2 ambient. It was further observed that the phase of the ALD-grown cobalt oxide thin film could be controlled by controlling the precursor or reactant pulsing condition. The study revealed that pure Co3O4 phase could be grown at a relatively low temperature (250 °C) by using water vapor as a reactant. Therefore, this work systemically demonstrated several pathways to grow single-phase Co3O4 by ALD using a novel metalorganic cobalt precursor.
Bibliographical noteFunding Information:
This work was supported by Mid-career Researcher Program through the National Research Foundation of Korea (NRF) ( 2015R1A2A2A04004945 ), the Priority Research Centers Program through the NRF funded by the Ministry of Education ( 2014R1A6A1031189 ), and the MOTIE (Ministry of Trade, Industry & Energy (# 10080651 ) and KSRC (Korea Semiconductor Research Consortium) support program for the development of the future semiconductor device. The precursor used in this study was provided by UP Chemical Co. Ltd., Korea.
© 2018 Elsevier B.V.
All Science Journal Classification (ASJC) codes
- Condensed Matter Physics
- Surfaces and Interfaces
- Surfaces, Coatings and Films
- Materials Chemistry