Knapp Caroline E, Prassides Iasson D, Sathasivam Sanjayan, Parkin Ivan P, Carmalt Claire J
Department of Chemistry, University College London, 20 Gordon Street, Christopher Ingold Laboratories, London, WC1H 0AJ (United Kingdom), Fax: (+44) (0)2076797463.
Chempluschem. 2014 Jan;79(1):122-127. doi: 10.1002/cplu.201300289. Epub 2013 Nov 24.
Copper-based spinel oxide CuGa O films have been deposited by means of a simple one-pot solution-based chemical vapour deposition (CVD) method. Aerosol-assisted (AA) CVD of copper(II) 2,2,6,6,-tetramethylheptan-3,5-dionate (thd), Cu(thd) and gallium(III) acetylacetonate, Ga(acac) , in toluene resulted in the formation of transparent films with a slight yellow tinge at 300-500 °C. Scanning electron microscopy (SEM) indicated that the films had grown by means of an island growth mechanism. Energy-dispersive X-ray (EDX) analysis and X-ray photoelectron spectroscopy (XPS) showed that CuGa O had formed along with copper(I) oxide and gallium(III) oxide was observed at the surface of the film. Annealing the films under a range of conditions (air, N , vacuum) resulted in oxidation and the formation of CuGa O and copper(II) oxide, as shown by powder X-ray diffraction (XRD). The films were further analysed by UV/Vis spectroscopy and atomic force microscopy. Similar AACVD depositions using copper(II) acetylacetonate, Cu(acac) , and Ga(acac) in a range of solvents only resulted in the formation of gallium oxide owing to the lower solubility of the copper precursor than the gallium complex. AACVD is dependent on the precursor solubility hence Cu(thd) is a superior precursor to Cu(acac) owing to its increased solubility.
基于铜的尖晶石氧化物CuGa₂O₄薄膜已通过一种简单的一锅法溶液基化学气相沉积(CVD)方法制备而成。在300 - 500°C下,以甲苯为溶剂,通过气溶胶辅助(AA)CVD法使2,2,6,6 - 四甲基庚烷 - 3,5 - 二酮铜(II)(thd),即Cu(thd)与乙酰丙酮镓(III),即Ga(acac)₃反应,形成了略带黄色调的透明薄膜。扫描电子显微镜(SEM)表明,这些薄膜是通过岛状生长机制生长的。能量色散X射线(EDX)分析和X射线光电子能谱(XPS)显示,薄膜表面除了形成CuGa₂O₄外,还观察到了氧化亚铜和三氧化二镓。如粉末X射线衍射(XRD)所示,在一系列条件(空气、氮气、真空)下对薄膜进行退火处理会导致氧化,并形成CuGa₂O₄和氧化铜。通过紫外/可见光谱和原子力显微镜对薄膜进行了进一步分析。在一系列溶剂中使用乙酰丙酮铜(II),即Cu(acac)₂和Ga(acac)₃进行类似的AA CVD沉积,由于铜前驱体的溶解度低于镓配合物,仅导致了氧化镓的形成。AA CVD取决于前驱体的溶解度,因此由于其溶解度增加,Cu(thd)是比Cu(acac)₂更优的前驱体。