作者：Arana-Chavez, D.;Toumayan, E.;Lora, F.;McCaslin, C.;Adomaitis, R.A.;

作者单位：Department of Chemical and Biomolecular Engineering, Institute for Systems Research, University of Maryland, College Park, MD 20742, United States;Department of Chemical and Biomolecular Engineering, Institute for Systems Research, University of Maryland,

刊名：Chemical vapor deposition

ISSN：0948-1907

出版年：2010-01-05

卷：16

期：41194

起页：336

止页：345

分类号：TQ175

语种：英文

关键词：Copper oxide;Mathematical modeling;PEC hydrogen production;Reaction equilibrium;Response;Surface models;

内容简介

In this paper we consider the CVD of copper oxide, a semiconductor with demonstrated potential for solar hydrogen production by the photo- electrochemical (PEC) splitting of water. Extensive experiments with a hot-wall CVD reactor and a cuprous iodide/oxygen precursor system are conducted, revealing unexpected film deposition patterns and temperature/oxygen partial pressure dependencies. An evolutionary sequence of mathematical models is developed to understand the observed behavior, starting with an empirical response surface model (RSM) to rigorously determine the trends indicated in the data. Then, a series of physics-based models are developed to gain a theoretical understanding of the thermodynamic, reaction, and chemical species transport mechanisms at work in this reactor. In contrast to previously published research where gas-phase reaction and particle nucleation were identified as the key processes, our model predictions suggest the deposition process is largely governed by surface reactions. Chemical vapor deposition of copper oxide films using a hot-wall tubular reactor and a cuprous iodide and oxygen precursor system is studied experimentally and by developing a sequence of empirical response surface models and physically based transport and deposition chemistry models. In particular, the source of an unusually sharp transition between distinct cuprous and cupric oxide phases is attributed to the O2 gradient resulting from the back-diffusion of this reactant and surface reactions producing the copper oxide films.