Synthesis And Characterization Of Lanthanide Complexes Bearing Hydrazone Ligands And The Preparation And Purification Of TEMAH/TEMAZ

With the development of integrated circuits, the conventional material SiO₂cannot meet therequirements of the gate dielectric material. The rare earth oxides are attracted widespread attention,owing to having a high dielectric constant （k （La₂O₃）=27, k （Gd₂O₃）=16） and excellentthermodynamic stability. The atomic layer deposition （ALD） can be applied in preparing high-qualityrare earth oxide film. The Key problem is the selection of suitable precursor with good properties.The main research work in this thesis is design, synthesis a series of Lanthanide/gadoliniumcomplexes （precursor） bearing hydrazones ligand. The complexes obtained were characterized byelemental analysis,1H NMR,13C{H} NMR and X-ray single crystal diffraction. The TG was alsoused to determine the thermal stability as well as the decomposition mechanism. The research workincludes the following two parts:Part one: Synthesis and characterization of hydrazones Lanthanide/gadolinium complexesHomoleptic rare-earth hydrazones complexes La[Ph（OCNNC）MePh]₃（2a）,La[Ph（OCNNC）MeEt]₃（2b）, La[Ph（OCNNC）C₅H₁₀]₃（2c）, Gd[Ph（OCNNC）MePh]₃（2d）,Gd[Ph（OCNNC）MeEt]₃（2e）, Gd[Ph（OCNNC）C₅H₁₀]₃（2f） were synthesized by using anhydrousLnCl₃（THF）x（Ln=La，Gd） reacting with3equiv of lithium hydrazones in THF. The complexesobtained were characterized by elemental analysis,1H NMR,13C{H} NMR spectroscopy. The thermalanalysis and decomposition mechanism of the complex2b was preliminarily studied byThemoGravimetry.Lanthanide and gadolinium complexes （PhCONNCMeC₆H₄）₂La₂[N（SiMe₃）₂]₂（THF）₂（3a）,La（PhCONNCCH₃Ph）₃（3b）,（PhCONNCC₅H₉）₂La₂[N（SiMe）₂]₂（THF）₂（3c）, La(PhCONNCC₅H₁₀)₃（3d）,（PhCONNCMeCHMe）₂La₂[N（SiCH₃）₂]₂（THF）₂（3e）, La（PhCONNCMeCHMe）₃（3f）,（PhCONNCMeC₆H₄）₂Gd₂[N（SiMe）₂]₂（3g）, Gd（PhCONNCMePh）₃（3h）,（PhCONNCC₅H₉）₂Gd₂[N（SiMe₃）₂]₂（THF）₂（3i）, Gd(PhCONNCC₅H₁₀)₃（3j）,（PhCONNCMeCHMe）₂Gd₂[N（SiCH₃）₂]₂（THF）₂（3k） and Gd（PhCONNCMeCHMe）₃（3l） weresynthesized by protolysis of Ln[N（SiMe₃）₂]₃with hydrazones. The complexes obtained werecharacterized by elemental analysis,1H NMR and13C{H} NMR spectroscopy. Complex3c、3e、3khave been characterized by X-ray single crystal analysis.Part two: Preparation and Purification of TEMAH/TEMAZ TEMAH and TEMAZ are good precursors for the deposition of ZrO₂and HfO₂high-k gatedielectric material. The key problem is the preparation and purification. In this part, the TEMAH andTEMAZ were synthesized using ZrCl4/HfCl4as starting material reacting with LiN（Me）Et. Thepurification method was also studied and the final purity of complound obtained reached4N.