The planar anodic Al2O3-ZrO2 nanocomposite capacitor dielectrics for advanced passive device integration.

The need for integrated passive devices (IPDs) emerges from the increasing consumer demand for electronic product miniaturization. Metal-insulator-metal (MIM) capacitors are vital components of IPD systems. Developing new materials and technologies is essential for advancing capacitor characteristics and co-integrating with other electronic passives. Here we present an innovative electrochemical technology joined with the sputter-deposition of Al and Zr layers to synthesize novel planar nanocomposite metal-oxide dielectrics consisting of ZrO2 nanorods self-embedded into the nanoporous Al2O3 matrix such that its pores are entirely filled with zirconium oxide. The technology is utilized in MIM capacitors characterized by modern surface and interface analysis techniques and electrical measurements. In the 95-480 nm thickness range, the best-achieved MIM device characteristics are the one-layer capacitance density of 112 nF·cm-2, the loss tangent of 4·10-3 at frequencies up to 1 MHz, the leakage current density of 40 pA·cm-2, the breakdown field strength of up to 10 MV·cm-1, the energy density of 100 J·cm-3, the quadratic voltage coefficient of capacitance of 4 ppm·V-2, and the temperature coefficient of capacitance of 480 ppm·K-1 at 293-423 K at 1 MHz. The outstanding performance, stability, and tunable capacitors' characteristics allow for their application in low-pass filters, coupling/decoupling/bypass circuits, RC oscillators, energy-storage devices, ultrafast charge/discharge units, or high-precision analog-to-digital converters. The capacitor technology based on the non-porous planar anodic-oxide dielectrics complements the electrochemical conception of IPDs that combined, until now, the anodized aluminum interconnection, microresistors, and microinductors, all co-related in one system for use in portable electronic devices.

Modification of yttrium alkoxides: ß-Ketoesterate-substituted yttrium alkoxo/hydroxo/oxo clusters.

Reaction of Y(5)O(OiPr)(13) ("yttrium iso-propoxide") with one molar equivalent of isopropyl acetoacetate (iprac) per Y resulted in the formation of Y(9)O(OH)(9)(OiPr)(8)(iprac)(8), a rare example of an yttrium alkoxo/hydroxo/oxo cluster. Reaction in a 1:3 molar ratio gave Y(4)(OH)(2)(iprac)(10) and Y(6)(OH)(6)(iprac)(12) instead. A fourth cluster, Y(9)O(OH)(9)(iprac)(16), structurally closely related to Y(9)O(OH)(9)(OiPr)(8)(iprac)(8), was obtained upon recrystallization of Y(4)(OH)(2)(iprac)(10) from CDCl(3).

From thioxo cluster to dithio cluster: exploring the chemistry of polynuclear zirconium complexes with S,O and S,S ligands.

Three different zirconium thio and oxothio clusters, characterized by different coordination modes of dithioacetate and/or monothioacetate ligands, were obtained by the reaction of monothioacetic acid with zirconium n-butoxide, Zr(O(n)Bu)4, in different experimental conditions. In particular, we isolated the three polynuclear Zr3(µ3-SSSCCH3)2(SSCCH3)6·2(n)BuOH (Zr3), Zr4(µ3-O)2(µ-η(1)-SOCCH3)2(SOCCH3)8(O(n)Bu)2 (Zr4), and Zr6(µ3-O)5(µ-SOCCH3)2(µ-OOCCH3)(SOCCH3)11((n)BuOH) (Zr6) derivatives, presenting some peculiar characteristics. Zr6 has an unusual star-shaped structure. Only sulfur-based ligands, viz., chelating dithioacetate monoanions and an unusual ethane-1,1,1-trithiolate group µ3 coordinating the Zr ions, were observed in the case of Zr3. 1D and 2D NMR analyses confirmed the presence of differently coordinated ligands. Raman spectroscopy was further used to characterize the new polynuclear complexes. Time-resolved extended X-ray absorption fine structure measurements, devoted to unraveling the cluster formation mechanisms, evidenced a fast coordination of sulfur ligands and subsequent relatively rapid rearrangements.

Clusters for alkyne-azide click reactions.

The clusters Ti(6)O(4)(OPr)(8)(OOC(CH(2))(2)C[triple bond]CH)(8) and [Zr(6)O(4)(OH)(4)(OOC(CH(2))(3)C[triple bond]CH)(12)](2) with acetylenic carboxylate ligands were prepared and structurally characterized in solution and in the crystalline state. Model reactions showed that they are suitable candidates for the formation of cluster-based inorganic-organic hybrid materials by alkyne-azide click reactions.

Modification of aluminium alkoxides with dialkylmalonates.

ABSTRACT: Depending on the reaction conditions, different aluminium dialkylmalonate derivatives were obtained by reaction of aluminium alkoxides Al(OR)3 (R = Et, iPr, tBu) with dialkylmalonates, viz. Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5. All compounds were characterized by NMR spectroscopy, and single crystal structure analyses are reported for each type of compound. An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio. Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate.