Chemical Technology 1, Institute of Chemistry , Carl von Ossietzky University Oldenburg , 26129 Oldenburg , Germany.
Inorg Chem. 2018 May 7;57(9):5133-5144. doi: 10.1021/acs.inorgchem.8b00204. Epub 2018 Apr 17.
A series of six cobalt ketoiminates, of which one was previously reported but not explored as a chemical vapor deposition (CVD) precursor, namely, bis(4-(isopropylamino)pent-3-en-2-onato)cobalt(II) ([Co( pki)], 1), bis(4-(2-methoxyethylamino)pent-3-en-2-onato)cobalt(II) ([Co(meki)], 2), bis(4-(2-ethoxyethylamino)pent-3-en-2-onato)cobalt(II) ([Co(eeki)], 3), bis(4-(3-methoxy-propylamino)pent-3-en-2-onato)cobalt(II) ([Co(mpki)], 4), bis(4-(3-ethoxypropylamino)pent-3-en-2-onato)cobalt(II) ([Co(epki)], 5), and bis(4-(3-isopropoxypropylamino)pent-3-en-2-onato)cobalt(II) ([Co( ppki)], 6) were synthesized and thoroughly characterized. Single-crystal X-ray diffraction (XRD) studies on compounds 1-3 revealed a monomeric structure with distorted tetrahedral coordination geometry. Owing to the promising thermal properties, metalorganic CVD of CoO was performed using compound 1 as a representative example. The thin films deposited on Si(100) consisted of the spinel-phase CoO evidenced by XRD, Rutherford backscattering spectrometry/nuclear reaction analysis, and X-ray photoelectron spectroscopy. Photoelectrochemical water-splitting capabilities of spinel CoO films grown on fluorine-doped tin oxide (FTO) and TiO-coated FTO revealed that the films show p-type behavior with conduction band edge being estimated to -0.9 V versus reversible hydrogen electrode. With a thin TiO underlayer, the CoO films exhibit photocurrents related to proton reduction under visible light.
一系列六种钴 ketoiminates，其中一种以前有报道但未作为化学气相沉积（CVD）前体进行探索，即双（4-（异丙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（pki）]，1），双（4-（2-甲氧基乙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（meki）]，2），双（4-（2-乙氧基乙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（eeki）]，3），双（4-（3-甲氧基丙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（mpki）]，4），双（4-（3-乙氧基丙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（epki）]，5）和双（4-（3-异丙氧基丙基氨基）戊-3-烯-2-酮基）钴（II）（[Co（ppki）]，6）被合成并进行了彻底的表征。化合物 1-3 的单晶 X 射线衍射（XRD）研究表明，它们具有单体结构和扭曲的四面体配位几何形状。由于具有有前途的热性能，使用化合物 1 作为代表性示例进行了 CoO 的金属有机 CVD。沉积在 Si（100）上的薄膜由 XRD、卢瑟福背散射光谱/核反应分析和 X 射线光电子能谱证实为尖晶石相 CoO。在掺氟氧化锡（FTO）和 TiO 涂覆的 FTO 上生长的尖晶石 CoO 薄膜的光电化学水分解能力表明，薄膜表现出 p 型行为，导带边缘估计为相对于可逆氢电极为-0.9 V。在薄的 TiO 底层的情况下，CoO 薄膜在可见光下显示与质子还原相关的光电流。
