Chemical Vapor Deposition of Metal‐Containing Thin‐Film Materials from Organometallic Compounds

Spencer, James T.

doi:10.1002/9780470166420.ch3

Cited by 52 publications

(6 citation statements)

References 475 publications

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“…The value of k 0 of a c4/a4 reaction of UL 2 (L ) 1, 2) is determined to be from 0.34 × 10 -3 (U2 2 on Pt) to 0.9-1.5 × 10 -2 cm s -1 (on GC). The order of the k 0 values are found to be similar to that of U(acac) 4 .…”

Section: Enhanced Stability and Et Kinetics Of Uo 2 L (L ) 1 2)mentioning

confidence: 57%

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

et al. 2007

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Acetylacetone shows dissociative electron transfer when it is complexed with metal ions. In an effort to improve the kinetics of electron transfer of uranium-based complexes for application to a redox-flow battery, improvement by dimerization of acetylacetone into tetraketones with potential chelate effect is examined and discussed quantitatively. For the monomer acetylacetone, electron transfer of uranium complexes reveals an ECE mechanism and an inner-sphere reaction on the electrode surface. By using tetraketones, 8-oxo-2,4,-12,14-tetraoxapentadecane and m-bis(2,4-dioxo-1-pentyl)benzene, the electron transfer of tetraketones with U(VI)/U(V) and U(IV)/U(III) shows rapid kinetics based on the E mechanism. In clear contrast to U(acac) 4 , the electrochemically reduced species of the U(IV) complex with tetraketone is stable during potential cycling. These results are also supported by NMR of tetraketones with U(VI) and U(IV); each acetylacetone site to uranium atom is stable at -40 ∼ +40 °C. The results demonstrate a remarkable enhancement of the stability of the reduced form of the metal center and thereby an improvement of the redox kinetics by the chelate effect. The tetraketones are eminently suitable for use in the active materials of a high-efficiency redox-flow battery.

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Section: Enhanced Stability and Et Kinetics Of Uo 2 L (L ) 1 2)mentioning

confidence: 57%

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

et al. 2007

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“…The volatility and low-temperature clean decomposition of various transition metal β-diketonates, such as those of manganese(III), make them suitable as metal organic chemical vapor deposition precursors . While there are many homometallic β-diketonates known as precursors for the preparation of oxide materials, heterometallic β-diketonato complexes are relatively rare . Zanello previously published the synthesis of various first row transition metal complexes of 1-ferrocenyl-1,3-butanedione, including the Mn(III) complex [Mn(FcCOCHCOCH 3 ) 3 ] ( 3b ) .…”

Section: Introductionmentioning

confidence: 99%

Consequences of Electron-Density Manipulations on the X-ray Photoelectron Spectroscopic Properties of Ferrocenyl-β-diketonato Complexes of Manganese(III). Structure of [Mn(FcCOCHCOCH₃)₃]

et al. 2016

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and 2d with 1. A single crystal X-ray structure determination of 3b (Z=2, triclinic, space group P-1) highlighted a weak axial elongating Jahn-Teller effect and a high degree of bond conjugation.An X-ray photoelectron spectroscopic study, by virtue of linear relationships between group electronegativities of ligand R groups, χ R , or χ R , and binding energies of both the Fe 2p 3/2 and Mn 2p 3/2 photoelectron lines, confirmed communication between molecular fragments of 2a-2d as well as 3a-3d. This unprecedented observation allows prediction of binding energies from known β-diketonato side group χ R values.Keywords: Manganese, ferrocene, betadiketonato complexes, substituent effects, electronic spectra, X-ray photoelectron spectroscopy, binding energy predictions. IntroductionThe first row transition metal, manganese, exhibits a wide variety of oxidation states in compounds ranging from Mn(I), e. we then highlight intramolecular communication between molecular fragments of 3a-3d from results of an X-ray photoelectron spectroscopic (XPS) study. Results and discussion Synthesis and characterizationThe ferrocene-containing manganese ( IR spectra of 3a-3d and 4 displayed the characteristic strong ν CO vibrations found between 1498-1572 cm -1 (Experimental Part) which is typical for chelate-bonded β-diketonato ligands in transition metal chemistry. 22 A shift to lower wave numbers is observed for 3a-3d and 4 compared to the free β-diketones 2a-2d (1620 -1710 cm -1 ) 23 which allows the monitoring of the reaction progress. Prominent CH-stretching bands are also observed at ca. 3100 cm -1 .Peak maxima of the UV-Vis spectra of complexes 3a-3d and 4 ( Figure 1) are summarized in Table 1. Dichloromethane solutions of the highly soluble complexes 3a-3c and 4 all showed relatively high extinction coefficients. All complexes followed the Beer-Lambert law, A = εCl, which implies a linear relationship between absorbance and concentration. Van der Zeiden 24 reported a similar lower energy band in tungsten(0) -diketonato complexes and assigned it to a MLCT band with destabilized t 2g level after appropriate calculations. Single Crystal X-ray structure of 3bTo understand the trends observed in XPS-obtained binding energies for Fe(II) (and also Mn(III)) of complexes 3a -3d described in the next section, an evaluation of the structural characteristics of 3b is useful. The fac isomer of complex 3b crystallized from toluene in the triclinic space group P-1 having ca. 1 disordered solvent molecule for every two molecules of 3b. The refinement parameters and crystal data are summarized in Table 2 and the molecular structure of 3b, highlighting atom labeling, are shown in Figure 2. Selected bond distances and bond angles are summarized in the caption of Figure 2, but the full set of bond lengths and angles is available in Supplementary Information.

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“…to form metal oxides and metal chalcogenides. 52,53 We also explored whether the second pathway might be operational or whether we could rule it out. The second pathway is indeed possible on thermodynamic grounds.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…First, two Cu(hfac)(vtms) molecules undergo the known metal-catalyzed disproportionation to form a Cu metal film, , and the volatile species Cu(hfac) 2 and 2 vtms, according to reaction : Second, HBr may oxidize the copper metal up to Cu + , resulting in CuBr and a reduced species, such as H 2 , according to reaction : We believe the first pathway to be likely by analogy to the many metalorganic precursor reactions with vapors of Brønsted acids (H 2 O, H 2 S, etc.) to form metal oxides and metal chalcogenides. , We also explored whether the second pathway might be operational or whether we could rule it out. The second pathway is indeed possible on thermodynamic grounds.…”

Section: Results and Discussionmentioning

confidence: 99%

Chemical Vapor Deposition of Transparent, p-Type Cuprous Bromide Thin Films

et al. 2021

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The semiconductors CuX (X = Cl, Br, or I) are high-mobility p-type transparent conductors, promising for use in thin film optoelectronic devices such as perovskite photovoltaics. These devices require smooth, pinhole free films that are tens of nanometers thick but uniform across tens of centimeters. Chemical vapor deposition (CVD), an established and scalable process, can provide excellent throughput, conformality, and uniformity on such large areas. However, no prior CVD method could produce continuous thin films of any cuprous halide. We have established such a method, preparing CuBr thin films by reaction between HBr gas and vinyltrimethylsilane(hexafluoroacetylacetonato)copper(I). Our method not only provides the desired device-quality films but also opens up the possibility of a general route to CVD of other metal halides.

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Chemical Vapor Deposition of Metal‐Containing Thin‐Film Materials from Organometallic Compounds

Cited by 52 publications

References 475 publications

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

Consequences of Electron-Density Manipulations on the X-ray Photoelectron Spectroscopic Properties of Ferrocenyl-β-diketonato Complexes of Manganese(III). Structure of [Mn(FcCOCHCOCH₃)₃]

Chemical Vapor Deposition of Transparent, p-Type Cuprous Bromide Thin Films

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Chemical Vapor Deposition of Metal‐Containing Thin‐Film Materials from Organometallic Compounds

Cited by 52 publications

References 475 publications

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect

Consequences of Electron-Density Manipulations on the X-ray Photoelectron Spectroscopic Properties of Ferrocenyl-β-diketonato Complexes of Manganese(III). Structure of [Mn(FcCOCHCOCH3)3]

Chemical Vapor Deposition of Transparent, p-Type Cuprous Bromide Thin Films

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Consequences of Electron-Density Manipulations on the X-ray Photoelectron Spectroscopic Properties of Ferrocenyl-β-diketonato Complexes of Manganese(III). Structure of [Mn(FcCOCHCOCH₃)₃]