Abstract
The oxygen surface exchange kinetics of mixed ionic and electronic conducting oxides (MIECs) play a critical role in the efficiency of intermediate-to-high-temperature electrochemical devices. Although there is increasing interest in low-temperature preparation of MIEC thin films, the impact of the resultant varied degrees of crystallinity on the surface exchange kinetics has not been widely investigated. Here, we probe the effect of crystallization on oxygen surface exchange kinetics in situ, by applying an optical transmission relaxation (OTR) approach during annealing of amorphous films. OTR enables contact-free, in situ, and continuous quantification of the oxygen surface exchange coefficient (k chem ); we previously applied it to Pr x Ce 1-x O 2-δ and SrTi 1-x Fe x O 3-δ thin films. In this work, the OTR approach was successfully extended to other mixed conducting thin film compositions for the first time (i.e., perovskite SrTi 0.65 Co 0.35 O 3-δ and Ruddlesden-Popper Sr 2 Ti 0.65 Fe 0.35 O 4±δ ), as well as to Pr 0.1 Ce 0.9 O 2-δ , enabling quantification of the k chem of their native surfaces and comparison of the behavior of films with different final crystal structures. All thin films were prepared by pulsed laser deposition at 25 or 700-800 °C and subject to subsequent thermal treatments with simultaneous OTR monitoring of k chem . The surface roughness, grain size, and crystallinity were evaluated by scanning probe microscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Fluorite Pr 0.1 Ce 0.9 O 2-δ films grown at 25 °C did not exhibit an increase in k chem after annealing, as they were already crystalline as grown at 25 °C. For all other compositions, OTR enabled in situ observation of both the crystallization process and the emergence of rapid surface exchange kinetics immediately upon crystallization. Perovskite SrTi 0.65 Co 0.35 O 3-δ and Ruddlesden-Popper Sr 2 Ti 0.65 Fe 0.35 O 4±δ thin films grown at 25 °C exhibited at least 1-2 orders of magnitude enhanced k chem after annealing compared with highly crystalline thin films grown at 800 °C, indicating the benefits of in situ crystallization.
| Original language | English |
|---|---|
| Pages (from-to) | 9102-9116 |
| Number of pages | 15 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 11 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - 6 Mar 2019 |
Bibliographical note
Funding Information:N.H.P. gratefully acknowledges financial support from the U.S. Department of Energy, Basic Energy Sciences through a DOE Early Career Award (grant # DE-SC00189). T.C. gratefully acknowledges funding from a JSPS Doctoral Fellowship (201702103). G.F.H. acknowledges a JSPS Kakenhi Grant-in-aid for Young Scientists (B) Award (No. JP16K18235) and the Progress-100 funding for Kyushu University-MIT collaboration. J.M. was supported for summer exchange research through the NSF-PIRE X-fusion project. K.S. and G.F.H. acknowledge the Center-of-Innovation program. The authors also acknowledge the International Institute for Carbon-Neutral Energy Research (WPI-I2CNER) at Kyushu University.
Publisher Copyright:
© 2019 American Chemical Society.
Keywords
- amorphous
- in situ crystallization
- optical absorption
- oxygen electrodes
- oxygen surface exchange
- thin films
ASJC Scopus subject areas
- General Materials Science