Highly Volatile, Low Melting, Fluorine-Free Precursors for Metal-Organic Chemical Vapor Deposition of Lanthanide Oxide-Containing Thin Films

Belot, John A.; Wang, Anchuan; McNeely, Richard J.; Liable‐Sands, Louise M.; Rheingold, Arnold L.; Marks, Tobin J.

doi:10.1002/(sici)1521-3862(199903)5:2<65::aid-cvde65>3.0.co;2-b

Cited by 32 publications

(18 citation statements)

References 11 publications

(17 reference statements)

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“…A key requirement for viable MOCVD processes is the availability of high-purity, thermally stable, volatile, and preferably low-melting metalorganic precursors having appropriate reactivity patterns to achieve efficient transport of the respective metal sources for clean film growth. Building on results from previous oxide growth studies, [26][27][28][29] known and new families of multidentate ligands that saturate the metal coordination sphere have been implemented in precursor synthesis and MOCVD growth of TCO films. Figure 4 illustrates several families of precursors that have been studied at Northwestern.…”

Section: Thin Films Of Transparent Conducting Oxidesmentioning

confidence: 99%

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

Freeman¹,

Poeppelmeier²,

Mason³

et al. 2000

MRS Bull.

322

182

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Transparent conducting oxides (TCOs) have been known and employed technologically for more than 50 years, primarily in the form of doped single-cation oxides such as In2O3 and SnO2. Beginning in the 1990s, however, multi-cation oxide TCOs began to be developed in Japan (see the article by Minami in this issue and the references therein) and at the former Bell Laboratories. Since then, new TCO phases are being reported with increasing frequency as technological interest in this area heightens. At the same time, our fundamental understanding of the chemical and structural origins of transparent conductivity continues to expand and promises a pathway to dramatically improved materials for a host of applications. This article describes a collaborative, multi-investigator bulk an d thin-film research effort at Northwestern University aimed at the synthesis, characterization, and enhanced understanding of multi-cation (compound and solidsolution) TCOs, and provides a brief account of what we are discovering about this important class of materials.

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Section: Thin Films Of Transparent Conducting Oxidesmentioning

confidence: 99%

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

Freeman¹,

Poeppelmeier²,

Mason³

et al. 2000

MRS Bull.

322

182

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“…Tris[ N , N -bis(trimethylsilyl)amido]lanthanide complexes (Ln[N(SiMe 3 ) 2 ] 3 , abbreviated here as Ln NTMS ) are encountered frequently in the lanthanide catalysis literature, both as precursors to more complex lanthanide organometallics − and as homogeneous catalysts, particularly for hydro-functionalization/reduction of alkenes and alkynes. − These complexes are commercially available for many lanthanides, or can be readily synthesized and purified, rendering them highly accessible and of great interest to the synthetic methods community. − A report from the Marks laboratory showed that it is possible to carry out the catalytic synthesis of amides with Ln NTMS , but the La NTMS -catalyzed reduction of amides had not yet been investigated. Given this, and the proven ability of La NTMS to catalyze carbonyl hydroboration, La NTMS -catalyzed amide hydroboration was an intriguing target.…”

Section: Introductionmentioning

confidence: 99%

La[N(SiMe₃)₂]₃-Catalyzed Deoxygenative Reduction of Amides with Pinacolborane. Scope and Mechanism

et al. 2020

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Tris[N,N-bis(trimethylsilyl)amide]lanthanum (LaNTMS) is an efficient and selective homogeneous catalyst for the deoxygenative reduction of tertiary and secondary amides with pinacolborane (HBpin) at mild temperatures (25–60 °C). The reaction, which yields amines and O(Bpin)2, tolerates nitro, halide, and amino functional groups well, and this amide reduction is completely selective, with the exclusion of both competing inter- and intramolecular alkene/alkyne hydroboration. Kinetic studies indicate that amide reduction obeys an unusual mixed-order rate law which is proposed to originate from saturation of the catalyst complex with HBpin. Kinetic and thermodynamic studies, isotopic labeling, and DFT calculations using energetic span analysis suggest the role of a [(Me3Si)2N]2La-OCHR(NR′2)[HBpin] active catalyst, and hydride transfer is proposed to be ligand-centered. These results add to the growing list of transformations that commercially available LaNTMS is competent to catalyze, further underscoring the value and versatility of lanthanide complexes in homogeneous catalysis.

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“…Several lanthanide diketonate adducts with polyethers (Drake et al 1993a,b;Bradley et al 1994;Baxter et al 1995) and lanthanide ketoiminates (Belot et al 1999) have been developed with a view to using them as precursors for the *Author for correspondence (shivu@mrc.iisc.ernet.in) deposition of thin films of lanthanide-containing oxides. Some of these adducts exhibit improved properties over the β-diketonates, in terms of thermal stability and volatility, and are of potential interest for application as MOCVD precursors.…”

Section: Introductionmentioning

confidence: 99%

Oriented growth of thin films of samarium oxide by MOCVD

Shalini

Shivashankar

2005

Bull Mater Sci

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Thin films of Sm 2 O 3 have been grown on Si(100) and fused quartz by low-pressure chemical vapour deposition using an adducted β β-diketonate precursor. The films on quartz are cubic, with no preferred orientation at lower growth temperatures (~ 550°C), while they grow with a strong (111) orientation as the temperature is raised (to 625°C). On Si(100), highly oriented films of cubic Sm 2 O 3 at 625°C, and a mixture of monoclinic and cubic polymorphs of Sm 2 O 3 at higher temperatures, are formed. Films grown on either substrate are very smooth and fine-grained. Infrared spectroscopic study reveals that films grown above 600°C are free of carbon.

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Highly Volatile, Low Melting, Fluorine-Free Precursors for Metal-Organic Chemical Vapor Deposition of Lanthanide Oxide-Containing Thin Films

Cited by 32 publications

References 11 publications

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

La[N(SiMe₃)₂]₃-Catalyzed Deoxygenative Reduction of Amides with Pinacolborane. Scope and Mechanism

Oriented growth of thin films of samarium oxide by MOCVD

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Highly Volatile, Low Melting, Fluorine-Free Precursors for Metal-Organic Chemical Vapor Deposition of Lanthanide Oxide-Containing Thin Films

Cited by 32 publications

References 11 publications

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

Chemical and Thin-Film Strategies for New Transparent Conducting Oxides

La[N(SiMe3)2]3-Catalyzed Deoxygenative Reduction of Amides with Pinacolborane. Scope and Mechanism

Oriented growth of thin films of samarium oxide by MOCVD

Contact Info

Product

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La[N(SiMe₃)₂]₃-Catalyzed Deoxygenative Reduction of Amides with Pinacolborane. Scope and Mechanism