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A series of heteroleptic strontium complexes (1-9) using a combination of different aminoalkoxides and 2,2,6,6-tetramethyl-3,5-heptanedionate (tmhd) were prepared to examine the effect of the bulkiness and coordination ability of the aminoalkoxide ligand in these complexes as well as potential strontium precursors. All complexes were characterized by FT-IR, FT-NMR, elemental analyses, and thermo-gravimetric (TG) analyses. The crystal structure analyses of 1, 2, 4, and 5 demonstrate their stability in the dimer form and the unwillingness of the strontium atom to form more than six coordination bonds in these complexes. The complex 5 shows an unusual picture: the existence of one hexa-coordinated and one penta-coordinated strontium atom side by side in its dimer structure. The introduction of ether groups as coordination sites in complexes 6-9 led to a decrease in steric hindrance which resulted in the formation of the complex 7 as a tetramer. The complex 7 shows a unique Sr4O4 cubane core where oxygen atoms undergo μ3-bridging between strontium atoms. The TG analyses show that the complexes exhibit a step-wise decomposition character, with the major mass losses in the region 150-400 °C.
A series of heteroleptic strontium complexes (1-9) using a combination of different aminoalkoxides and 2,2,6,6-tetramethyl-3,5-heptanedionate (tmhd) were prepared to examine the effect of the bulkiness and coordination ability of the aminoalkoxide ligand in these complexes as well as potential strontium precursors. All complexes were characterized by FT-IR, FT-NMR, elemental analyses, and thermo-gravimetric (TG) analyses. The crystal structure analyses of 1, 2, 4, and 5 demonstrate their stability in the dimer form and the unwillingness of the strontium atom to form more than six coordination bonds in these complexes. The complex 5 shows an unusual picture: the existence of one hexa-coordinated and one penta-coordinated strontium atom side by side in its dimer structure. The introduction of ether groups as coordination sites in complexes 6-9 led to a decrease in steric hindrance which resulted in the formation of the complex 7 as a tetramer. The complex 7 shows a unique Sr4O4 cubane core where oxygen atoms undergo μ3-bridging between strontium atoms. The TG analyses show that the complexes exhibit a step-wise decomposition character, with the major mass losses in the region 150-400 °C.
Heteroleptic complexes of strontium () were prepared by employing β-diketonates and donor-functionalized alkoxides as coordinating ligands. The results illustrate the effect of alkoxide substituent groups on the overall structures of the complexes. The presence of a terminal methoxy group in the alkoxide ligands leads to the formation of trimeric complexes , whereas the substituents on the amine nitrogen prove to have less influence in determining the structure. The attempts to increase steric bulkiness of the aminoalkoxide ligands by introducing ethyl groups on the amine nitrogen and to the alkoxy carbon did not lead to a structural change from the dimeric form in but resulted in structurally interesting strontium complexes. In trimeric complexes , the three strontium atoms were held together by two μ3-O bonds using alkoxide oxygen atoms and two μ2-O bonds using a combination of alkoxide and β-diketonate ligand oxygens. The strontium metal centers in these complexes exhibit seven-coordination states in and , whereas exhibits one six-coordinated and two seven-coordinated strontium metals in its structure. All of the complexes were characterized using FT-NMR, FT-IR, elemental analyses, and thermogravimetric (TG) analyses.
Recently, NiO film of metal-oxide-metal (MOM) structure 1a has drawn much attention because it shows reproducible resistance switching phenomena applicable to next generation nonvolatile resistive random access memory (ReRAM) device. The resistance switching phenomenon, that is, a drastic change in resistance between a high-resistance state (OFFstate) and low resistance state (ON-state) in current-voltage (I-V) characteristic of MOM structure, has been observed in binary oxides such as NiO, 1 TiO 2 , 2 Nb 2 O 5 , 3 Cr-doped SrZrO 3 , 4 Pr 1-x CaMnO 3 , 5 and chalcogenide semiconductors although exact origin was unsolved. Among these materials, the binary oxide is the first consideration for the application due to the relatively simple fabrication process.In the case of a device fabrication, the self-limiting process of atomic layer deposition (ALD) may be very important for the growth of NiO films because the expected structure of ReRAM device requires the filling process of NiO on the hole or trench-patterned 3-dimensional substrates. Therefore, it is worthwhile to find the optimal ALD process for NiO film growth by using suitable Ni precursors. In general, most of Ni compounds are in solid state at room temperature although highly volatile liquid precursor is highly desirable to obtain conformal film qualities in ALD processes.A number of nickel precursors have been synthesized and examined for preparing Ni and NiO films using metal organic chemical vapor deposition (MOCVD) and ALD during the past years. The ligands for the nickel precursors are carbonyl, 6 β-diketonates, 7 cycolpentadienyl, 8 and alkoxides, 9 N,N'-dialkylacetamidinates, 10 phosphites, 11 and combination of cyclopentadienyl and allyl.12 Many nickel precursors have their drawbacks such as low volatilities and toxicity, and carbon contaminations in the prepared films. Except Ni(CO) 4 , all of them are solids at room temperature, although cyclopentadienylallylnickel for nickel thin films is a liquid at 10 ºC.12 HubertPfalzgraf et al. prepared a volatile Ni(OCHMeCH 2 NMe 2 ) 2 which was sublimed at 93-95 °C under 0.01 mmHg.13 Recently, we have synthesized nickel dialkylamino alkoxide complexes [Ni(dmamp) 2 , Ni(emamp) 2 , and Ni(deamp) 2 ] which are solids at room temperature but they are volatile and thermally stable. 14In this study, novel volatile and liquid nickel precursors were synthesized by using ligands with unsymmetrical substituents and employed with water to deposit NiO films by ALD. In addition, the resistance switching of Pt/NiO/Pt MIM structure was also investigated.Metal complexes with low melting point, that is, liquid precursors are highly desirable to keep a constant vapor pressure and to avoid particle problems during the deposition process. As our ongoing studies to develop volatile and stable precursors applicable to chemical deposition processes such as CVD and ALD, we have introduced dialkylamino alkoxide ligands which contain alkoxide and donor-functionalized amino group to saturate the vacant sites of the central metal io...
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