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用于通过大气压燃烧化学气相沉积工艺沉积金属氧化物薄膜的钴和锰羧酸盐。

Cobalt and manganese carboxylates for metal oxide thin film deposition by applying the atmospheric pressure combustion chemical vapour deposition process.

作者信息

Kretzschmar B S M, Assim K, Preuß A, Heft A, Korb M, Pügner M, Lampke T, Grünler B, Lang H

机构信息

Innovent e.V. Prüssingstraße 27B 07745 Jena Germany

Technische Universität Chemnitz, Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry 09107 Chemnitz Germany

出版信息

RSC Adv. 2018 Apr 25;8(28):15632-15640. doi: 10.1039/c8ra02288g. eCollection 2018 Apr 23.

Abstract

Coordination complexes [M(OCCHOCHOMe)] (M = Co, 4; M = Mn, 5) are accessible by the anion exchange reaction between the corresponding metal acetates [M(OAc)(HO)] (M = Co, 1; M = Mn, 2) and the carboxylic acid HOCCHOCHOMe (3). IR spectroscopy confirms the chelating or μ-bridging binding mode of the carboxylato ligands to M(ii). The molecular structure of 5 in the solid state confirms a distorted octahedral arrangement at Mn(ii), setup by the two carboxylato ligands including their α-ether oxygen atoms, resulting in an overall two-dimensional coordination network. The thermal decomposition behavior of 4 and 5 was studied by TG-MS, revealing that decarboxylation occurs initially giving [M(CHOCHOMe)], which further decomposes by M-C, C-O and C-C bond cleavages. Complexes 4 and 5 were used as CCVD (combustion chemical vapour deposition) precursors for the deposition of CoO, crystalline MnO and amorphous MnO thin films on silicon and glass substrates. The deposition experiments were carried out using three different precursor solutions (0.4, 0.6 and 0.8 M) at 400 °C. Depending on the precursor concentration, particulated layers were obtained as evidenced by SEM. The layer thicknesses range from 32 to 170 nm. The rms roughness of the respective films was determined by AFM, displaying that the higher the precursor concentration, the rougher the CoO surface is (17.4-43.8 nm), while the manganese oxide films are almost similar (6.2-9.8 nm).

摘要

通过相应的金属乙酸盐[M(OAc)(H₂O)](M = Co,1;M = Mn,2)与羧酸HOC₂H₂CO₂Me(3)之间的阴离子交换反应,可以得到配位络合物[M(OC₂H₂CO₂Me)](M = Co,4;M = Mn,5)。红外光谱证实了羧基配体与M(ii)的螯合或μ-桥连结合模式。固态下5的分子结构证实了Mn(ii)处扭曲的八面体排列,由两个羧基配体及其α-醚氧原子构成,形成了一个整体的二维配位网络。通过TG-MS研究了4和5的热分解行为,结果表明最初发生脱羧反应生成[M(C₂H₂CO₂Me)],其进一步通过M-C、C-O和C-C键的断裂而分解。络合物4和5用作CCVD(燃烧化学气相沉积)前驱体,用于在硅和玻璃基板上沉积CoO、结晶MnO和非晶MnO薄膜。使用三种不同浓度(0.4、0.6和0.8 M)的前驱体溶液在400 °C下进行沉积实验。扫描电子显微镜(SEM)显示,根据前驱体浓度的不同,得到了颗粒状的层。层厚度范围为32至170 nm。通过原子力显微镜(AFM)测定了各薄膜的均方根粗糙度,结果表明前驱体浓度越高,CoO表面越粗糙(17.4 - 43.8 nm),而氧化锰薄膜的粗糙度几乎相似(6.2 - 9.8 nm)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0138/9080101/935dcadab57f/c8ra02288g-f1.jpg

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