Synthesis And Film-Forming Properties Of N-containing Mn(Ⅱ) Complexes

Manganese-based thin film materials are widely used in lithium ion batteries,supercapacitors,magnetoresistors,microelectronics,etc.due to their stability,giant magnetism,capacitance reversibility and eco-friendliness.With the continuous development of technology,more demanding requirements for film materials have been put forwarded.Among the current reported thin film deposition methods,the films deposited by chemical vapor deposition（CVD）and atomic layer deposition（ALD）processes exhibit the best performance.Precursors are the basis of CVD and ALD technologies according to their principles.The different structure of precursors will greatly affect their chemical reactivity and thermal properties,which leads to a large difference in the film deposition process,such as the film deposition rate and the performance of the film.Moreover,there are some drawbacks in the current reported ALD/CVD manganese precursors,including the limited amounts,the single structure,and the low deposition rate for the ALD process.In view of the above problems,this paper developed a variety of novel manganese complexes,and their potential as ALD/CVD precursors was evaluated by the deposition experiments.The research results could provide more choices towards manganese precursors for people,and solved the low growth rate of the ALD processes reported so far.The specific research contents are as follows:（1）Six kinds of nitrogen-containing ethyl amidinate manganese（Ⅱ）complexes with high reactivity were designed and synthesized,and their thermochemical properties were studied.Due to the difference in the introduction of functional groups,the thermochemical properties of manganese（Ⅱ）complexes were different and presented a"structural-effect".These six nitrogen-containing ethyl amidinate manganese（Ⅱ）complexes could satisfy the requirements for ALD/CVD processes.（2）Based on the above studies,the bis（N,N’-di-tert-butylethenyl amidinate）manganese（Ⅱ）complex was used as a precursor for depositing MnO_x films by ALD technology combined with O₃ and H₂O as the co-reactants in this paper.The effect on the properties of the film was investigated by changing the deposition process parameters.The results showed that the ethyl amidinate manganese（Ⅱ）complex can be used as a precursor of ALD,and the corresponding ALD process exhibited a high growth rate（4.7?/cycle and 2.1?/cycle）owing to the high reactivity of the used precursor.（3）Due to the unstability towards moisture and oxygen of the nitrogen-containing ethyl amidinate manganese（Ⅱ）complexes,three nitrogen-containing manganese（Ⅱ）complexes with similar amidinate structures were synthesized to improve the above mentioned drawback,and their thermal properties and applicable as CVD precursors were studied.The results demonstrated that the complexes possessed excellent volatility and thermal stability,which meet the requirements of CVD processes.Moreover,the MnSi_xO_y films were successfully deposited through CVD technology using the bis（2-trimethylsilylaminopyridine）manganese（Ⅱ）complex as a precursor and O₂ as a co-reagent,and the deposited MnSi_xO_y films exhibited high purity.